EA024710B1 - Electrochemical hydroxide systems and methods using metal oxidation - Google Patents

Abstract

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

Description

In one aspect, a method is provided comprising contacting the anode with an anode electrolyte (anolyte), the anolyte comprising a metal ion; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the cathode electrolyte (catholyte); and conducting a reaction of an unsaturated hydrocarbon or saturated hydrocarbon with an anolyte containing a metal ion of a higher oxidation state in an aqueous medium; while the aqueous medium contains more than 5 wt.% water.

In one aspect, a method is provided comprising contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte and adding a ligand to the anolyte, while the ligand interacts with a metal ion.

In some embodiments of the above aspects, the method further comprises generating alkali, water, or hydrogen gas at the cathode. In some embodiments of the aforementioned aspects, the method further comprises alkali formation at the cathode. In some embodiments of the above aspects, the method further comprises generating hydrogen gas at the cathode. In some embodiments of the above aspects, the method further comprises generating water at the cathode. In some embodiments of the above aspects, the cathode is an oxygen depolarization cathode that reduces oxygen and water to hydroxide ions. In some embodiments of the aforementioned aspects, the cathode is a hydrogen gas producing cathode on which water is reduced to hydrogen gas and hydroxide ions. In some embodiments of the aforementioned aspects, the cathode is a hydrogen gas producing cathode on which hydrochloric acid is reduced to hydrogen gas. In some embodiments of the above aspects, the cathode is an oxygen depolarization cathode on which hydrochloric acid reacts with gaseous oxygen to produce water.

In some embodiments of the above aspects and embodiments, the list of metal ions includes, but is not limited to, iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium , gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combinations thereof. In some embodiments, the list of metal ions includes, but is not limited to, iron, chromium, copper, and tin. In some embodiments, the metal ion is copper. In some instances, 1,024,710 locations have a lower oxidation state of the metal ion equal to 1+, 2+, 3+, 4+, or 5+. In some embodiments, the higher oxidation state of the metal is 2+, 3+, 4+, 5+, or 6+. In some embodiments, the metal ion is copper, which transfers from Cu + to Cu ² +; a metal ion is iron, which transfers from Fe ²⁺ to Fe ³⁺ ; the metal ion is tin, which passes from the 8n + ² to 8u ^4+; the metal ion is chromium, which transfers from Cr ²⁺ to Cr ³⁺ ; a metal ion is platinum, which passes from Ρΐ ²⁺ to Ρΐ ⁴⁺ ; or a combination thereof.

In some embodiments of the above aspects and embodiments, no gas is used or it does not form at the anode.

In some embodiments of the above aspects and embodiments, the method further comprises adding a ligand to the anolyte; in this case, the ligand interacts with a metal ion.

In some embodiments of the aforementioned aspects and embodiments, the method further comprises reacting an unsaturated hydrocarbon or saturated hydrocarbon with an anolyte containing a highly oxidized metal ion and a ligand; in this case, the reaction proceeds in an aqueous medium.

In some embodiments of the aforementioned aspects and embodiments, the reaction of an unsaturated hydrocarbon or saturated hydrocarbon with an anolyte containing a higher oxidation metal ion is a halogenation or sulfonation using a higher oxidation metal halide or sulfate and leads to the formation of a halogenated or sulfonated hydrocarbon, respectively, and a metal halide or sulfate in a lower oxidation state. In some embodiments, the lower oxidized metal halide or sulfate is recycled back to the anolyte.

In some embodiments of the aforementioned aspects and embodiments, the anolyte comprising a metal with a higher oxidation state further comprises a metal ion with a lower oxidation state.

In some embodiments of the aforementioned aspects and embodiments, the unsaturated hydrocarbon is a compound of formula I which, after halogenation or sulfonation, leads to the formation of a compound of formula II (K) t-SpN {: p.t1 ->

I p where η is 2-10; t is 0-5; C.] is 1-5;

K is independently selected from hydrogen, halogen, —COOC ′, —OH and —ΝΚ ′ (Κ), where K ′ and K are independently selected from hydrogen, alkyl, and substituted alkyl;

X is a halogen selected from chlorine, bromine and iodine; -8O ₃ N or -O8O ₂ OH.

In some embodiments, t is 0; η is 2; with | equal to 2 and X represents chlorine. In some embodiments, the compound of formula I is ethylene, propylene or butylene; and the compound of formula II is ethylene dichloride, propylene dichloride or 1,4-dichlorobutane, respectively. In some embodiments, the method further comprises forming a vinyl chloride monomer from ethylene dichloride and forming poly (vinyl chloride) from a vinyl chloride monomer.

In some embodiments of the aforementioned aspects and embodiments, a saturated hydrocarbon is a compound of formula III, and by halogenation or sulfonation, a compound of formula IV t is formed.

U) k'C _n H (2 ₀₊ ;}. ^ (^) K * С _n Н0 _{в +} ; ^ ₊ ,)

III IV where η is 2-10; k is 0-5;

equal to 1-5;

K is independently selected from hydrogen, halogen, —COOC ′, —OH and —ΝΚ ′ (Κ), where K ′ and K are independently selected from hydrogen, alkyl, and substituted alkyl;

X is a halogen selected from chlorine, bromine and iodine; -8O ₃ N or -O8O ₂ OH.

In some embodiments, the compound of formula III is methane, ethane or propane.

In some embodiments of the aforementioned aspects and exemplary embodiments, the aqueous medium co-0242710 holds 5 to 90% by weight of water.

In some embodiments of the aforementioned aspects and embodiments, the ligand provides one or more of the following properties, including, but not limited to, increased reactivity of a metal ion with respect to an unsaturated hydrocarbon, saturated hydrocarbon, or hydrogen gas; increased selectivity of the metal ion with respect to halogenation of unsaturated or saturated hydrocarbons; increased halogen transfer from the metal ion to an unsaturated hydrocarbon, saturated hydrocarbon or hydrogen gas; reduced redox potential of the electrochemical cell; increased solubility of the metal ion in the aquatic environment; reduced transition of the metal ion through the membrane into the catholyte of the electrochemical cell; reduced corrosion of the electrochemical cell and / or reactor; increased separation of the metal ion from the acidic solution after reaction with hydrogen gas; increased separation of the metal ion from the halogenated hydrocarbon solution; and their combination.

In some embodiments of the above aspects and embodiments, the ligand includes, but is not limited to, substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and combinations thereof.

In some embodiments of the above aspects and examples of embodiments, the ligand has the formula A

IN

IN

And in which η and m are independently 0-2;

K and K ¹ independently represent H, alkyl or substituted alkyl.

In some embodiments, substituted alkyl is alkyl substituted with one or more groups selected from alkenyl, halogen, amine, and substituted amine.

In some embodiments of the above aspects and embodiments, the ligand has the formula C

in which K independently represents O, 8, P or Ν; η is 0 or 1.

In some embodiments of the above aspects and examples of embodiments, the ligand has the formula Ό or is an oxide of this compound

where K ¹ , K ² and K ³ independently represent H, alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amine, substituted amine, cycloalkyl, substituted cycloalkyl, heterocycloalkyl and substituted heterocycloalkyl.

In some embodiments of the above aspects and embodiments, the ligand has the formula E

in which K ¹ and K ² independently represent H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amine, substituted amine, cycloalkyl, substituted cycloalkyl, heterocycloalkyl and substituted heterocycloalkyl.

In some embodiments of the above aspects and embodiments, the ligand has the formula P

- 3,024,710

IN

G in which K represents hydrogen, alkyl or substituted alkyl; η is 0-2; t is 0-3; to is 1-3.

In one aspect, a device is provided comprising an anode in contact with an anolyte containing a metal ion; wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with an unsaturated hydrocarbon or saturated hydrocarbon in an aqueous medium; while the aqueous medium contains more than 5 wt.% water.

In one aspect, a device is provided comprising an anode in contact with an anolyte containing a metal ion; moreover, the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; the ligand in the anolyte, while the ligand is able to interact with a metal ion; and the cathode in contact with the catholyte.

In some embodiments of the above aspects and embodiments, the device further includes a ligand in the anolyte; while the ligand is able to interact with a metal ion.

In some embodiments of aspects and embodiments of the aforementioned device, the cathode is a gas diffusion cathode configured to react oxygen gas and water to form hydroxide ions. In some embodiments of the aspects and embodiments of the aforementioned device, the cathode is a hydrogen gas producing cathode configured to form hydrogen gas and hydroxide ions through water reduction. In some embodiments of the aspects and embodiments of the aforementioned device, the cathode is a hydrogen gas producing cathode adapted to recover an acid, such as hydrochloric acid, to hydrogen gas. In some embodiments of the aspects and embodiments of the above device, the cathode is a gas diffusion cathode configured to react hydrochloric acid and oxygen to form water.

In some embodiments of aspects and embodiments of the aforementioned device, the anode is configured such that no gas is generated.

In some embodiments of the above aspects and embodiments, the device further includes a precipitant configured to contact the catholyte with divalent cations to form a product in the form of carbonate and / or bicarbonate.

In some embodiments of the aforementioned aspects and embodiments, the apparatus further includes a reactor operably coupled to the anode compartment and configured to react an anolyte containing a higher oxidation metal ion and a ligand with an unsaturated hydrocarbon or saturated hydrocarbon in an aqueous medium.

In some embodiments of the above aspects and examples of embodiments, the metal ion is copper. In some embodiments of the above aspects and embodiments, the unsaturated hydrocarbon is ethylene.

In another aspect, a method is provided comprising contacting the anode with anolyte; oxidation of a metal ion at the anode, from a lower oxidation state to a higher oxidation state; and bringing the cathode into contact with the catholyte; the cathode is an oxygen depolarization cathode and oxidizes oxygen and water to hydroxide ions.

In another aspect, a method is provided comprising contacting the anode with anolyte and oxidizing a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte and obtaining hydroxide ions in catholyte; and bringing the catholyte into contact with gaseous carbon dioxide or a solution containing bicarbonate / carbonate ions.

In another aspect, a method is provided comprising contacting the anode with anolyte and oxidizing a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and preventing the migration of metal ions from the anolyte to the catholyte by using a size-exclusion membrane or an anion exchange membrane.

In another aspect, a method is provided comprising contacting the anode with anolyte and oxidizing a metal ion at the anode from a lower oxidation state to a higher oxidation state; and bringing the cathode into contact with the catholyte and obtaining hydroxide ions and / or hydrogen gas at the cathode; and acid production by reacting a metal ion with a higher oxidation state with 4,407,710 hydrogen gas.

In another aspect, a method is provided comprising supplying a voltage below 2.5 V; bringing the anode into contact with the anolyte and oxidizing the metal ion at the anode from a lower oxidation state to a higher oxidation state; and bringing the cathode into contact with the catholyte; wherein the cathode produces hydroxide ions, hydrogen gas, or water.

In another aspect, there is provided a method for producing a green (obtained by environmentally friendly technology) halogenated hydrocarbon comprising contacting the anode with anolyte and oxidizing metal chloride on the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and halogenating the unsaturated hydrocarbon with a higher oxidation metal chloride to produce a green halogenated hydrocarbon.

In one aspect, a method is provided comprising contacting the anode with anolyte and oxidizing metal chloride at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; halogenation of an unsaturated hydrocarbon with a metal chloride in a higher oxidation state; and adding a ligand to the metal chloride, wherein the ligand interacts with the metal ion.

The text of this description provides several examples of embodiments of the above aspects. In some embodiments, the cathode is a gas diffusion cathode. In some embodiments, the cathode forms hydrogen gas during the reduction of water or hydrochloric acid. In some embodiments, the metal ion is selected from the group consisting of iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium , platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combinations thereof. In some embodiments, the metal ion is selected from the group consisting of iron, chromium, copper and tin. In some embodiments, the metal ion is copper. In some embodiments, the metal ion is tin. In some embodiments, the metal ion is chromium. In some embodiments, the metal ion is iron. In some embodiments, the lower oxidation state of the metal ion is 1+, 2+, 3+, 4+, or 5+. In some embodiments, the higher oxidation state of the metal ion is 2+, 3+, 4+, 5+, or 6+. In some embodiments, the metal ion is copper, which is converted in the anode compartment from Cu + to Cu ² +. In some embodiments, the metal ion is iron, which is converted in the anode compartment from Fe ²⁺ to Fe ³⁺ . In some embodiments, the metal ion is tin, which is converted in the anode compartment from § ² + to § ⁴⁺ . In some embodiments, the metal ion is chromium, which is converted in the anode compartment from Cg ³⁺ to Cg ⁶⁺ . In some embodiments, the metal ion is chromium, which is converted in the anode compartment from CA to C '.' A In some embodiments, no gas is used at the anode or no gas is formed at the anode. In some embodiments, no acid is formed in the anode compartment. In some embodiments, the metal ion is in the form of a metal halide. In some embodiments, the metal oxide halide with a higher oxidation state, possibly containing a metal halide with a metal oxidation state of a lower oxidation state, is brought into contact with hydrogen gas to produce hydrogen halide, for example, but not limited to, hydrogen chloride, chloride hydrogen acid, hydrogen bromide, hydrobromic acid, hydrogen iodide or hydrogen iodide, as well as a metal halide with a metal ion in a lower oxidation state. In some embodiments, a metal halide with a lower oxidation metal ion is recycled back to the anode compartment. In some embodiments, a higher oxidation metal halide with a metal ion, possibly containing a lower oxidation metal halide, is contacted with an unsaturated hydrocarbon and / or saturated hydrocarbon to produce a halogenated hydrocarbon and a metal halide with a metal ion in lower oxidation state. In some embodiments, a metal halide with a lower oxidation metal ion is recycled back to the anode compartment.

In some embodiments, a higher oxidation metal chloride with a metal ion, possibly containing a lower metal oxidation metal chloride, is contacted with hydrogen gas to produce hydrochloric acid and a lower metal ion oxidation. In some embodiments, the metal chloride with the lower oxidation metal ion is recycled back to the anode compartment. In some embodiments, a higher oxidation metal chloride metal, possibly containing a lower oxidation metal chloride metal, is contacted with an unsaturated hydrocarbon to form a chlorinated hydrocarbon and a lower oxidation metal chloride metal ion. In some embodiments, the metal chloride with the lower oxidation metal ion is recycled back to the anode compartment. In some embodiments, the unsaturated hydrocarbon is ethylene, and a halogenated hydrocarbon, such as a chlorinated hydrocarbon, is ethylene dichloride. In some embodiments, the method described herein further comprises forming vinyl chloride monomer from ethylene dichloride. IN

- 5,024,710 in some embodiments, the method described herein further comprises forming poly (vinyl chloride) from the vinyl chloride monomer.

In some embodiments, the method further comprises contacting the catholyte with carbon from a carbon source. In some embodiments, the method further comprises contacting the catholyte with carbon selected from carbon dioxide gas obtained in an industrial process or a carbon dioxide solution from a gas-liquid contactor in contact with carbon dioxide gas from an industrial process. In some embodiments, the method further includes, after being contacted with carbon, contacting the catholyte with divalent cations to form a carbonate and / or bicarbonate product. In some embodiments, the method includes applying a voltage of from 0.01 to 2.5 V between the anode and cathode.

In some embodiments, the treatment of a metal ion of a higher oxidation state with an unsaturated hydrocarbon occurs inside the anode compartment. In some embodiments, the treatment of a metal ion at a higher oxidation state with an unsaturated hydrocarbon occurs outside the anode compartment. In some embodiments, treating the metal ion at a higher oxidation state with an unsaturated hydrocarbon results in the formation of a chlorinated hydrocarbon. In some embodiments, the chlorinated hydrocarbon is ethylene dichloride. In some embodiments, the method further comprises treating the Cu ² ′ ions with ethylene to form ethylene dichloride. In some embodiments, the method further comprises treating ethylene dichloride to form a vinyl chloride monomer. In some embodiments, the method further comprises treating the vinyl chloride monomer to form poly (vinyl chloride).

In another aspect, there is provided a device comprising an anode compartment, including an anode in contact with a metal ion located in the anolyte, wherein the anode compartment is configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment, including a cathode with oxygen depolarization in contact with the catholyte, while the cathode compartment is configured to produce alkali.

In another aspect, there is provided a device comprising an anode compartment comprising an anode in contact with a metal ion in an anolyte, the anode compartment configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; a cathode compartment comprising a cathode in contact with the catholyte, wherein the cathode compartment is configured to produce alkali; and a contact device operably connected to the cathode compartment and configured to contact carbon from a carbon source with catholyte.

In another aspect, there is provided a device comprising an anode compartment, including an anode in contact with a metal ion located in the anolyte, wherein the anode compartment is configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment comprising a cathode in contact with the catholyte, wherein the cathode compartment is configured to produce alkali; and a size exclusion membrane and / or anion exchange membrane configured to prevent the migration of the metal ion from the anolyte to the catholyte.

In another aspect, a device is provided comprising an anode in contact with an anolyte, wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably connected to the anode compartment and configured to react a metal ion of a higher oxidation state with hydrogen gas to form an acid.

In another aspect, a device is provided comprising an anode in contact with an anolyte, wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably coupled to the anode compartment and configured to react a metal ion of a higher oxidation state with an unsaturated hydrocarbon to form a green halogenated hydrocarbon.

In another aspect, a device is provided comprising an anode in contact with an anolyte, wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; the ligand in the anolyte, while the ligand is able to interact with a metal ion; and a reactor operably connected to the anode compartment and configured to react a metal ion of a higher oxidation state with an unsaturated hydrocarbon in the presence of this ligand.

Some embodiments of the aspects of the apparatus described above are provided herein. In some embodiments, the cathode is a gas diffusion cathode. In some embodiments, the cathode is configured to produce hydrogen gas in water reduction. In some embodiments, the device further includes an oxygen gas evolution system operatively coupled to the cathode compartment and configured to provide oxygen gas from the oxygen gas source to the cathode compartment. In some embodiments, the metal ion is in the form of a metal chloride. In some embodiments, the device further includes a reactor operably connected to the anode compartment and configured to

- 6,024,710 contacting the metal chloride and the metal ion, which is in a higher oxidation state, with an unsaturated hydrocarbon to form a chlorinated hydrocarbon. In some embodiments, the device further includes a contact device operably connected to the cathode compartment and configured to contact carbon from the carbon source with catholyte. In some embodiments, the device further includes a contact device operably connected to the cathode compartment and configured to contact carbon from the carbon source with catholyte; wherein carbon from the carbon source is selected from gaseous carbon dioxide from an industrial process or a solution of carbon dioxide from a gas-liquid contactor in contact with gaseous carbon dioxide from an industrial process. In some embodiments, the device further includes a precipitant for bringing the catholyte into contact with alkaline earth metal ions to form a β-carbonate and / or bicarbonate product.

In one aspect, there is provided a device comprising an anode compartment in which the anode compartment includes an anode in contact with a metal ion located in the anolyte, wherein the anode compartment is configured to transfer the metal ion from a lower oxidation state to a higher oxidation state, and a supply system unsaturated hydrocarbon, configured to supply an unsaturated hydrocarbon to the anode compartment. In some embodiments, the unsaturated hydrocarbon is ethylene. In some embodiments, the metal ion is a copper ion.

Brief Description of the Drawings

New features of the present invention are shown, in particular, in the attached claims. You can better understand the distinguishing features and advantages of the present invention with reference to the following detailed description, which shows illustrative embodiments in which the principles of the present invention are used, and the accompanying drawings, in which the following is presented.

FIG. 1A is an illustration of one embodiment of the present invention.

FIG. 1B is an illustration of one embodiment of the present invention.

FIG. 2 is an illustration of one embodiment of the present invention.

FIG. ZA is an illustration of one example embodiment of the present invention.

FIG. SV is an illustration of one example embodiment of the present invention.

FIG. 4A is an illustration of one example embodiment of the present invention.

FIG. 4B is an illustration of one example embodiment of the present invention.

FIG. 5A is an illustration of one example embodiment of the present invention.

FIG. 5B is an illustration of one embodiment of the present invention.

FIG. 5C is an illustration of one example embodiment of the present invention.

FIG. 6 is an illustration of one embodiment of the present invention.

FIG. 7A is an illustration of one example embodiment of the present invention.

FIG. 7B is an illustration of one example embodiment of the present invention.

FIG. 7C is an illustration of one embodiment of the present invention.

FIG. 8A is an illustration of one example embodiment of the present invention.

FIG. 8B is an illustration of one example embodiment of the present invention.

FIG. 8C is an illustration of one example embodiment of the present invention.

FIG. 9 is an illustration of one embodiment of the present invention.

10A is an illustration of one example embodiment of the present invention. 10B is an illustration of one example embodiment of the present invention.

is an illustration of one example embodiment of the present invention.

is an illustration of one example embodiment of the present invention.

is an illustration of one example embodiment of the present invention.

is a diagram of the experimental setup described in this text is a diagram of the experimental setup described in this text is a diagram of the experimental setup described in this text

FIG.

FIG.

FIG.

FIG.

FIG.

FIG. Example 1 FIG. Example 2 of FIG. example Z.

FIG. 17A is an illustrative graph for the reduction of chromium by gaseous hydrogen described in this text in Example 4.

FIG. 17B is an illustrative graph for the reduction of copper with gaseous hydrogen described in this text in Example 4.

FIG. 18 is an illustrative graph described in this text in Example 5.

FIG. 19 is an illustrative graph described in this text in Example 5.

FIG. 20 is an illustrative embodiment described in this text in example 6.

- 7,024,710

FIG. 21 is an illustrative graph described in this text in Example 7.

FIG. 22 is an illustrative graph described in this text in Example 8.

FIG. 23 illustrates a summary of DC resistance measurements of anion exchange membranes as described in Example 9.

FIG. 24 illustrates the suppression of the transition of a copper ion due to anion-exchange membranes, as described in example 9.

FIG. 25A illustrates several examples of ligands used in the reaction described in example 10.

FIG. 25B illustrates several examples of ligands that can be used in the reaction described in example 10.

FIG. 26 is an illustrative graph described in this text in Example 11.

FIG. 27 is an illustrative graph described in this text in Example 12.

FIG. 28 is an illustrative graph described in this text in Example 13.

FIG. 29 is an illustrative graph described in this text in Example 14.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are devices and methods related to the oxidation of a metal ion at the anode in the anode compartment, where the metal ion is oxidized from a lower oxidation state to a higher oxidation state.

As one skilled in the art understands, this electrochemical device and method can be organized using an alternative, equivalent saline solution, for example, potassium chloride solution or sodium chloride solution or magnesium chloride solution or sodium sulfate solution or ammonium chloride solution, to obtain an equivalent alkaline solution, for example, potassium hydroxide and / or potassium carbonate and / or potassium bicarbonate or sodium hydroxide and / or sodium carbonate and / or sodium bicarbonate or magnesium hydroxide and / or magnesium carbonate in catholyte. Accordingly, such equivalents are included in the scope of this patent application, to the extent that such equivalents are based on, or are intended to be based on, this device and method.

Before this invention will be described in more detail, it should be understood that the invention is not limited to the specific described examples of embodiments, since such examples, of course, may vary. It should also be understood that the terminology used in the text of this description is intended only to describe specific examples of embodiment, and is not intended to limit the invention, since the scope of the invention is limited only by the attached claims.

Where a range of values is given, it should be understood that each intermediate value, up to a tenth of a unit of the lower limit, unless the context clearly indicates otherwise, between the upper and lower limits of this range, as well as any other reduced or intermediate value in the specified range, included in this invention. The upper and lower limits of these smaller ranges can independently be included in these smaller ranges, and are also included in this invention, with the exception of any specifically excluded limit in the specified range. If the specified range includes one or both limits, ranges excluding either or both of these included limits are also included in this invention.

Some ranges that are represented in the text of this description by numerical values can be defined as approximate numerical values. The term approximate should provide a rigorous basis for the exact number it is facing, as well as a value that is close to or approximately equal to the number that the term is before. In determining whether any value is close to or approximately equal to the specified value, the close or approximate uncompensated value may be a value that, in the context in which it is presented, provides essentially the equivalent of the specified value.

Unless otherwise specified, all technical and scientific terms used in the text of this description have the meaning that is usually implied by specialists in the field to which this invention relates. Although any methods and materials similar to or equivalent to the methods and materials described herein may be used in the implementation or verification of the present invention, representative illustrative methods and materials will be described below.

All publications and patents cited in this description are incorporated into this description by reference, as if it were specifically and individually indicated that each individual publication or patent is incorporated by reference, and they are incorporated into the text of this description by

- 8,024,710 references to disclose and describe the methods and / or materials in connection with which these publications are cited. Any publication is cited to describe it before the date of registration, and this should not be construed as an assumption that the present invention is not eligible for patenting due to the fact that this publication is dated retroactively due to the previous invention. In addition, publication dates shown may differ from actual publication dates, which may require independent confirmation.

It should be noted that used in the text of this description and in the attached claims, the singular forms include the plural, unless the context clearly indicates otherwise. In addition, it should be noted that the claims can be made in such a way as to exclude any optional element. As such, it is believed that this statement serves as a prerequisite for the use of such exclusive terminology as exclusively, only, etc., in connection with the enumeration of the elements of the claims or the use of a negative restriction.

As will be appreciated by those skilled in the art when reading this description, each of the individual embodiment examples described and illustrated in this text includes discrete components and distinctive features that can easily be distinguished from the distinctive features of any of several other embodiment examples or combined with them without leaving beyond the scope or essence of the present invention. Any cited method can be carried out in the cited order of events, or in any other order that is logically possible.

Compositions, methods and devices.

In one aspect, methods and devices are provided that relate to the oxidation of metal ions from a lower oxidation state to a higher oxidation state in the anode compartment of an electrochemical cell. The obtained metal ions in a higher oxidation state can be used in the form in which they are obtained, or they can be used for commercial purposes, for example, but not limited to, for chemical synthesis reactions, reduction reactions, etc. In one aspect, the electrochemical cells described herein provide an efficient and low voltage device in which a metal compound obtained, for example, a metal halide, such as metal chloride, or a metal with a higher oxidation state, can be used for other purposes, for example , but not limited to, for the production of hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydrogen iodide or sulfuric acid from gas different hydrogen and / or for the preparation of halogenated or sulfonated hydrocarbon of hydrocarbons.

The term halogenated hydrocarbons, as used throughout this specification, includes hydrocarbons substituted with halogen, where the halogen can be any number of halogens that can be attached to the hydrocarbon based on the allowable valency. Halogens include fluorine, chlorine, bromine and iodine. Examples of halogenated hydrocarbons include chloro derivatives of hydrocarbons, bromo derivatives of hydrocarbons and iodo derivatives of hydrocarbons. Chlorine derivatives of hydrocarbons include, but are not limited to, monochlorocarbons, dichlorocarbons, trichlorocarbons, etc. With regard to metal halides, such as, but not limited to, metal bromide and metal iodide, the bromide or metal iodide with a higher oxidation state obtained in the anode compartment can be used for other purposes, for example, without limitation, to produce hydrogen bromide or hydrogen iodide, and / or the production of bromine derivatives or iodine derivatives of hydrocarbons, for example, but not limited to, monobromohydrocarbons, dibromohydrocarbons, tribromohydrocarbons, monoiodohydrocarbons, diiodohydrocarbons, triiodocarbons hydrogens etc. In some embodiments, a higher oxidation metal ion can be sold as it is on the commercial market.

The term sulfonated hydrocarbons, as used in the text of this description, includes hydrocarbons substituted with one or more groups of § О ₃ H or-O ₈ O ₂ OH, based on the allowable valency.

The electrochemical cell of the present invention may be any electrochemical cell in which a metal ion of a lower oxidation state is converted in the anode compartment to a metal ion of a higher oxidation state. In such electrochemical cells, the cathodic reaction can be any reaction in which alkali is formed or not formed in the cathode compartment. Such a cathode absorbs electrons and carries out any reaction, including, but not limited to, the reaction of water with the formation of hydroxide ions and hydrogen gas, or the reaction of gaseous oxygen and water with the formation of hydroxide ions, or the reduction of protons from an acid, for example, chloride hydrogen acid to form hydrogen gas, or the reaction of protons from hydrochloric acid and oxygen gas to form water.

In some embodiments, the electrochemical cells may include alkali in the cathode compartment of the cell. The alkali obtained in the cathode compartment can be used as such for commercial purposes, or it can be treated with divalent cations to obtain divalent cations of carbonates / bicarbonates. In some embodiments, the alkali obtained in the cathode 9 024 710 compartment can be used to isolate or trap carbon dioxide. Carbon dioxide may be present in flue gases emitted by various industrial enterprises. Carbon dioxide can be isolated in the form of products - carbonates and / or bicarbonates. In some embodiments, the combination of a metal, with a metal with a higher oxidation state, can be taken from the anode compartment and used for any commercial process that is known to those skilled in the art. Thus, both anolyte and catholyte can be used to produce products that can be used for commercial purposes, thus providing a more economical, efficient and less energy-intensive process.

In some embodiments, the metal compound obtained in the anode compartment can be used as it is, or it can be purified before it is reacted with hydrogen gas, an unsaturated hydrocarbon, or a saturated hydrocarbon to produce hydrogen chloride, hydrogen acid, hydrogen bromide, hydrobromic acid, hydrogen iodide or hydroiodic acid, sulfuric acid and / or a halogenated hydrocarbon or sulfonated hydrocarbon, respectively about. In some embodiments, the metal compound can be used at the site of hydrogen gas generation and / or, in some embodiments, the metal compound selected from the anode compartment can be transferred to the place where hydrogen gas is generated, and hydrogen chloride, hydrochloric acid, is obtained from it, hydrogen bromide, hydrobromic acid, hydrogen iodide or hydroiodic acid. In some embodiments, a metal compound can be obtained in an electrochemical device and used in the place where the unsaturated hydrocarbon is received (or transported), for example, but not limited to, gaseous ethylene; and / or in some embodiments, the metal compound taken from the anode compartment may be transferred to the place where the unsaturated hydrocarbon is received (or transported), for example, but not limited to gaseous ethylene, and a halogenated hydrocarbon, for example a chlorinated hydrocarbon, is formed from it. In some embodiments, the ethylene gas generating device is combined with the electrochemical device of the present invention to simultaneously produce a higher oxidation metal and ethylene gas and to react between them to form a product, for example, ethylene dichloride (EDC). Ethylene dichloride can also be known as 1,2-dichloroethane, dichloroethane, 1,2-ethylene dichloride, glycol dichloride, Freon 150, drilling fluid (Ltot 8o1), brocide (LtosMe), Ge81tho1 Ltot-8o1, dichloro-emulsion, Dutch oil ( ) or granosan (dtapocap). In some embodiments, the electrochemical device of this invention is combined with a plant for producing vinyl chloride monomer (MVX) or a plant for producing polyvinyl chloride (PVC), so as to use the EDC obtained using the devices and methods of this invention in the production of MVX or PVC.

The electrochemical devices and methods described herein provide one or more advantages over traditional electrochemical devices known in the art, including (but not limited to) the absence of the need for a gas diffusion anode; higher cell efficiency; lower voltages; platinum free anodes; carbon dioxide insulation; green and environmentally friendly chemicals; and / or obtaining various commercially valuable products.

The devices and methods of this invention provide an electrochemical cell that produces various products, for example (but not limited to), metal salts obtained at the anode; metal salts used to produce various other chemicals; alkali obtained at the cathode; alkali used to obtain various other products; and / or hydrogen gas produced at the cathode. All such products were defined in the text of this description, and they can be called green chemicals, since such chemicals are obtained using an electrochemical cell that operates at low voltage or energy and with high efficiency. The low-voltage or less energy-intensive process described in this text can lead to lower carbon dioxide emissions compared to traditional methods for the manufacture of similar chemicals or products. In some embodiments, chemicals or products are obtained by trapping carbon dioxide from the flue gas with an alkali formed at the cathode, for example (but not limited to) carbon products and bicarbonates are obtained. Such products - carbonates and bicarbonates are green chemicals, as they reduce emissions and provide a cleaner environment.

Metal.

The terms metal ion or metal used in the text of this description include any metal ion that can be converted from a lower oxidation state to a higher oxidation state. Examples of metal ions include, but are not limited to, iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum , rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and their combinations. In some embodiments, metal ions include, but are not limited to, iron, copper, tin, chromium, or combinations thereof. In some embodiments, the metal ion

- 10,047,710 is copper. In some embodiments, the metal ion is tin. In some embodiments, the metal ion is iron. In some embodiments, the metal ion is chromium. In some embodiments, the metal ion is platinum. The term oxidation state used in this text includes the oxidation state of an atom in a substance. For example, in some embodiments, the oxidation state is the total charge of the ion. Some examples of reactions of metal ions on the anode are given below in table. I (SVE stands for standard hydrogen electrode). The theoretical values of the anode potential are also given. It should be understood that, depending on conditions, pH, electrolyte concentrations, etc., the actual values may slightly differ from these values, and such deviations are also included in the scope of this invention.

Table I

Anode reaction Anode potential, V (relative to SVE) Hell * - Hell ² * + e ' -1.98 Co ⁴ * - »Co ⁴ * + 8 -1.82 Pb ⁴ * - Pb ⁴ * + 2e ' -1.69 Ce ³ * - »Ce ⁴ * + e ' -1.44 2CG * + 7H ₂ O -> Cr ₂ O ₇ ⁴ '+ 14H * + be' -1.33 ΤΙ * - »ΤΙ ³ * + 2е ' -1.25 Nd ₂ ⁴ * - + 2Nd ⁴ * + 2e -0.91 Re ⁴ * - Re ³ * + e ' -0.77 V ³ * + H ₂ O - νθ ^{ζ +} + 2H * + e ' -0.34 and ⁴⁺ + 2n ₂ o -> io ² * + 4n ⁺ + e -0.27 Βϊ * ΒΪ ³ * + 2e ' -0.20 3ι ³ * + Н ₂ О - »ТУ ⁴ * + 2Н * + е ' -0.19 C * -> C ⁴ * + e -0.16 and about? - io ₂ ²⁺ + e ' -0.16 5p ² * - 5p ⁴ * + 2e ' -0.15 Ρ! Υ (ΝΗ ₃ ) _β ⁴ * -> P! And (NН ₃ ) ® ³ * + е -0.10 V ² * V ³ * + e ' +0.26 Her ⁴ * -> Her ³ * + e ' +0.35 Cg ⁴ * Cg ³ * + e ' +0.42 and ³ * and ⁴ * + e ' +0.52

A metal ion may be present as a metal compound or as a metal alloy or a combination thereof. In some embodiments, the metal-coupled anion is the same as the electrolyte anion. For example, in the case of using sodium or potassium chloride as an electrolyte, metal chloride is used as a metal compound, for example, but not limited to, iron chloride, copper chloride, tin chloride, chromium chloride, etc. For example, in the case of using sodium or potassium sulfate as an electrolyte, metal sulfate is used as a metal compound, for example, but not limited to, iron sulfate, copper sulfate, tin sulfate, chromium sulfate, etc. For example, in the case of using sodium or potassium bromide as an electrolyte, metal bromide is used as a metal compound, for example, but not limited to, iron bromide, copper bromide, tin bromide, etc.

In some embodiments, the electrolyte anion may be partially or completely different from the metal anion. For example, in some embodiments, the electrolyte anion may be sulfate, while the metal anion may be chloride. In such embodiments, it may be desirable to have a lower concentration of chloride ions in the electrochemical cell. For example, in some embodiments, a higher concentration of chloride ions in the anolyte, due to the presence of electrolyte chloride and metal chloride, can lead to the appearance of undesirable ionic particles in the anolyte. This can be avoided by using an electrolyte that contains ions other than chloride. In some embodiments, the anolyte may be a combination of ions similar to a metal anion and anions other than a metal ion. For example, if the metal anion is chloride, the anolyte may be a mixture of sulfate ions as well as chloride ions. In such embodiments, it may be desirable to have a sufficient concentration of chloride ions in the electrolyte to dissolve the metal salt, but not so high as to cause the formation of undesirable ionic particles.

In some embodiments, the electrolyte and / or metal compound is selected based on the desired end product. For example, if during the reaction between hydrogen gas and a metal compound, it is desirable to obtain HC1, then metal chloride is used as a metal compound, and sodium chloride is used as an electrolyte. For example, if it is desirable to obtain brominated hydrocarbon in the reaction between a metal compound and a hydrocarbon, then metal bromide is used as the metal compound, and sodium or potassium bromide is used as the electrolyte.

In some embodiments, the metal ions used in the electrochemical devices described herein can be selected based on the solubility of the metal in the anolyte and / or cell voltages, which are desirable for metal oxidation from a lower oxidation state to a higher oxidation state. For example, the voltage required for the oxidation of St ²⁴ to St ³⁴ may be lower than

- 11,024,710 voltage required to convert δη ²⁺ to δη ⁴⁺ ; however, the amount of HC1 formed by the reaction of hydrogen gas with Cr ³ may be lower than the amount of HC1 formed in the case of δη ⁴⁺ , since two chlorine atoms are produced per tin molecule. Thus, in some embodiments in which lower cell voltages may be desired, oxidation of a metal ion can be used, which results in a lower cell voltage, for example, but not limited to Cr ²⁺ . For example, for reactions in which carbon dioxide is trapped in the alkali obtained in the catholyte, a lower voltage may be desirable. In some embodiments, where it may be desirable to obtain a larger amount of a product, for example, hydrochloric acid, a metal ion can be used, for example (but not limited to), δη ²⁺ , which leads to a higher amount of product, although it can be used relatively higher voltages. For example, the cell voltage for a system with tin may be higher compared to a system with chromium, however, the concentration of acid formed in the case of δη ⁴⁺ can compensate for the higher voltage of the system. It should be understood that the products obtained using the devices and methods described in this text, for example, acid, halogenated hydrocarbons, sulfonated hydrocarbons, carbonates, bicarbonates, etc., are still green chemicals because they are made using less energy-intensive processes compared with the energy costs required for known traditional methods for producing the same products.

In some embodiments, a metal ion of a lower oxidation state and a metal ion of a higher oxidation state may be present in the anolyte. In some embodiments, it may be desirable to have a metal ion in the anolyte both in the lower oxidation state and in the higher oxidation state. Suitable ratios of the metal ion to a lower oxidation state and a higher oxidation state in the anolyte are described herein. A mixture of a metal ion in a lower oxidation state with a metal ion in a higher oxidation state can contribute to lowering the voltage in electrochemical devices and increasing the yield and selectivity of the corresponding catalytic reactions with hydrogen gas or hydrocarbons.

In some embodiments, the metal ion in the anolyte is a mixture of metal ions. For example, an anolyte containing a copper ion in a lower oxidation state and a copper ion in a higher oxidation state may also contain another metal ion, for example, but not limited to, iron. In some embodiments, the presence of a second metal ion in the anolyte, in combination with a catalytic reaction, can provide advantages in reducing the total energy of the electrochemical reaction.

Some examples of metal compounds that can be used in the devices and methods of this invention include, but are not limited to, copper sulfate (11), copper nitrate (11), copper chloride (1), copper bromide (1), copper iodide (1) , iron sulfate (111), iron nitrate (111), iron chloride (11), iron bromide (11), iron iodide (11), tin sulfate (11), tin nitrate (11), tin chloride (11), bromide tin (11), tin iodide (11), chromium sulfate (111), chromium nitrate (III), chromium chloride (11), chromium bromide (11), chromium iodide (11), zinc chloride (11), zinc bromide ( 11) etc.

Ligands.

In some embodiments, an additive, for example, a ligand, is used in combination with a metal ion to increase the oxidation efficiency of the metal ion inside the anode compartment and / or to improve the catalytic reactions of the metal ion inside / outside the anode compartment, for example (but not limited to) reaction with hydrogen gas, with an unsaturated hydrocarbon and / or with a saturated hydrocarbon. In some embodiments, a ligand is added to the anolyte together with the metal. In some embodiments, the ligand is attached to a metal ion. In some embodiments, the ligand is attached to the metal ion by covalent, ionic and / or coordination bonds. In some embodiments, the ligand is attached to a metal ion due to Van der Waals forces.

Accordingly, in some embodiments, methods are provided that include contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; adding a ligand to the anolyte, wherein the ligand interacts with a metal ion; and bringing the cathode into contact with the catholyte. In some embodiments, methods are provided that include contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; adding a ligand to the anolyte, wherein the ligand interacts with a metal ion; and bringing the cathode into contact with the catholyte, wherein the cathode produces hydroxide ions, water and / or hydrogen gas. In some embodiments, methods are provided that include contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; adding a ligand to the anolyte, wherein the ligand interacts with a metal ion; bringing the cathode into contact with the catholyte, while the cathode produces hydroxide ions, water and / or hydrogen gas; and bringing an anolyte containing a ligand and a metal ion in a higher oxidation state into contact with an unsaturated hydrocarbon, hydrogen gas, saturated hydrocarbon, or a combination thereof.

In some embodiments, methods are provided that include contacting the anode with anolyte; oxidation of the metal halide at the anode from a lower oxidation state to a higher oxidation state; adding a ligand to a metal halide, wherein the ligand interacts with an ion

- 12,024,710 metal; bringing the cathode into contact with the catholyte, while the cathode produces hydroxide ions, water and / or hydrogen gas; and halogenation of an unsaturated and / or saturated hydrocarbon with a metal oxidizer of a higher oxidation state. In some embodiments, the metal halide is metal chloride, and the halogenation reaction is chlorination. In some embodiments, such methods include a cathode producing hydrogen gas. In some embodiments, such methods include an oxygen depolarization cathode. In some embodiments, the unsaturated hydrocarbon in such methods is a substituted or unsubstituted alkene, such as C _p H _2n , where η is 2-20, (or alkine, or a compound of formula I, as is further described herein), for example, ethylene, propylene, butene, etc. In some embodiments, the saturated hydrocarbon in such methods is a substituted or unsubstituted alkane, such as C _p H _2p + ₂ , where η is 2-20 (or a compound with formula III, as is further described herein), for example methane, ethane, propane, etc. In some embodiments, the metal in such methods is a metal chloride, for example copper chloride. In some embodiments, such methods result in overall energy savings of more than 100 kJ / mol or more than 150 kJ / mol or more than 200 kJ / mol or from 100 to 250 kJ / mol; or this method leads to a voltage savings of more than 1 V (as described below and in Fig. 8C). In some embodiments, the unsaturated hydrocarbon in such methods is a C ₂ -C ₅ alkene, for example, but not limited to, ethylene, propylene, isobutylene, 2 butene (cis and / or trans), pentene, etc .; or C ₂ -C ₄ alkene, for example, but not limited to, ethylene, propylene, isobutylene, 2-butene (cis and / or trans), etc. In some embodiments, the unsaturated hydrocarbon in such methods is ethylene, and the metal ion in such methods is metal chloride, for example, copper chloride. In such methods, the halogenation of ethylene leads to the formation of EDC. In some embodiments, the saturated hydrocarbon in such methods is ethane, and the metal ion in such methods is metal chloride, for example, platinum chloride or copper chloride. In such methods, the halogenation of ethane leads to the formation of chloroethane or EDC.

In some embodiments, devices are provided that include an anode in contact with the anolyte; wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; the ligand in the anolyte, while the ligand is able to interact with a metal ion; and the cathode in contact with the catholyte. In some embodiments, devices are provided that include an anode in contact with the anolyte, wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; the ligand in the anolyte, while the ligand is able to interact with a metal ion; and a cathode in contact with the catholyte, wherein the cathode is configured to produce hydroxide ions, water and / or hydrogen gas. In some embodiments, devices are provided that include an anode in contact with the anolyte, wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; the ligand in the anolyte, while the ligand is able to interact with a metal ion; and the cathode in contact with the catholyte, wherein the cathode is configured to form hydroxide ions, water and / or hydrogen gas; and a reactor configured to react an anolyte containing a ligand and a metal ion of a higher oxidation state with an unsaturated hydrocarbon, hydrogen gas, saturated hydrocarbon, or a combination thereof. In some embodiments, such devices include an oxygen depolarization cathode. In some embodiments, such devices include a cathode producing hydrogen gas. In some embodiments, such devices result in overall energy savings of more than 100 kJ / mol or more than 150 kJ / mol or more than 200 kJ / mol or from 100 to 250 kJ / mol; or this device leads to a voltage savings of more than 1V (as described below and in Fig. 8C). In some embodiments, the unsaturated hydrocarbon in such devices is a C ₂ -C ₅ alkene, for example, but not limited to, ethylene, propylene, isobutylene, 2-butene (cis and / or trans), pentene, etc .; or C ₂ -C ₄ alkene, for example, but not limited to, ethylene, propylene, isobutylene, 2-butene (cis and / or trans), etc. In some embodiments, the unsaturated hydrocarbon in such devices is ethylene. In some embodiments, the metal in such devices is metal chloride, for example, copper chloride. In some embodiments, the unsaturated hydrocarbon in such devices is ethylene, and the metal ion in such devices is metal chloride, for example, copper chloride. In such devices, halogenation of ethylene leads to the formation of EDC. In some embodiments, the saturated hydrocarbon in such devices is ethane, and the metal ion in such devices is metal chloride, for example platinum chloride, copper chloride, etc. In such devices, the halogenation of ethane leads to the formation of chloroethane and / or EDC.

In some embodiments, the presence of a ligand leads to one or more of the following phenomena: increased reactivity of the metal ion with respect to the unsaturated hydrocarbon, saturated hydrocarbon, or hydrogen gas; increased selectivity of the metal ion with respect to the halogenation of unsaturated or saturated hydrocarbons; increased halogen transfer from the metal ion to an unsaturated hydrocarbon, saturated hydrocarbon or hydrogen gas; reduced redox potential of the electrochemical cell; increased solubility of the metal ion in the aquatic environment; reduced transition of the metal ion through

- 13,024,710 membrane in the catholyte of the electrochemical cell; reduced corrosion of the electrochemical cell and / or reactor; increased separation of the metal ion from the acidic solution after the reaction with hydrogen gas (for example, in the case of size-exclusion membranes); increased separation of the metal ion from the halogenated hydrocarbon solution (for example, in the case of size exclusion membranes); and their combination.

In some embodiments, the attachment of the ligand to the metal ion increases the size of the metal ion sufficiently to prevent it from migrating through the ion exchange membranes in the cell. In some embodiments, an anion exchange membrane can be used in combination with a size exclusion membrane in an electrochemical cell to prevent the migration of a metal ion attached to the ligand from the anolyte to the catholyte. Such membranes are described below. In some embodiments, the addition of a ligand to a metal ion increases the solubility of the metal ion in an aqueous medium. In some embodiments, the attachment of the ligand to the metal ion reduces the corrosion of metals in the electrochemical cell, as well as in the reactor. In some embodiments, the attachment of the ligand to the metal ion increases the size of the metal ion sufficiently to facilitate the separation of the metal ion from the acid or from the halogenated hydrocarbon after the reaction. In some embodiments, the presence and / or attachment of the ligand to the metal ion can prevent the formation of various halogenated metal ions in the solution and contribute to the formation of only the desired particles. For example, the presence of a ligand in a copper ion solution can limit the formation of various halogenated copper ions, for example, not limited to, [CuC1 ₃ ] ^2- or CuC1 ₂ ⁰ , but contribute to the formation of Cu ²⁺ / Cu ⁺ ion. In some embodiments, the presence and / or addition of a ligand in a metal ion solution reduces the overall cell voltage by providing one or more of the above advantages.

The term ligand used in the text of this description includes any ligand capable of improving the properties of a metal ion. In some embodiments, the ligand includes, but is not limited to, substituted or unsubstituted aliphatic phosphine, substituted or unsubstituted aromatic phosphine, substituted or unsubstituted amino phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted cyclic nitrogen-containing compound unsubstituted aliphatic sulfur-containing compound, substituted or unsubstituted cyclic sulfur-containing compound, substituted or unsubstituted heterocyclic compound; and substituted or unsubstituted heteroaromatic compound. Some examples of ligands are illustrated in FIG. 20, 25A and 25B.

Substituted or unsubstituted aliphatic nitrogen-containing compound.

In some embodiments, the ligand is a substituted or unsubstituted aliphatic nitrogen-containing compound of formula A

BUT

BUT

And where η and m are independently 0-2;

K and K ¹ independently represent H, alkyl or substituted alkyl.

In some embodiments, the alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or pentyl. In some embodiments, substituted alkyl is alkyl substituted with one or more groups, including alkenyl, halogen, amine, substituted amine, and combinations thereof. In some embodiments, the substituted amine is substituted with a group selected from hydrogen and / or alkyl. Some examples of ligands are illustrated in FIG. twenty.

In some embodiments, the ligand is a substituted or unsubstituted aliphatic nitrogen-containing compound of the formula B

IN

In which K and K ¹ independently represent H, alkyl or substituted alkyl.

In some embodiments, the alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or pentyl. In some embodiments, substituted alkyl is alkyl substituted with one or more groups, including alkenyl, halogen, amine, substituted amine, and combinations thereof. In some embodiments, the substituted amine is substituted with a group selected from hydrogen and / or alkyl.

In some embodiments, the ligand is a substituted or unsubstituted aliphatic nitrogen-containing donor compound of formula B in which K and K ¹ independently are H, C ₁ -C ₄ alkyl, or substituted C ₁ -C ₄ alkyl. In certain embodiments, C ₁ -C ₄ alkyl is methyl, ethyl, propyl, isopropyl, butyl or isobutyl. In certain embodiments, substituted alkyl C ₁ -C ₄ alkyl represents a C ₁ -C ₄ substituted by one or more groups including alkenyl, halogen, amine, substituted amine, and combinations thereof. In some embodiments, the substituted amine is substituted with a group selected from hydrogen and / or C ₁ -C ₃ alkyl.

The ligand concentration can be selected based on various parameters, including (but not limited to) the concentration of the metal ion, the solubility of the ligand, etc. Some examples of ligands that are substituted or unsubstituted aliphatic nitrogen-containing compounds are illustrated in FIG. twenty.

Substituted or unsubstituted crown ethers with heteroatoms O, 8, P or N.

In some embodiments, the ligand is a substituted or unsubstituted crown ether of formula C

where K independently represents O, 8, P or Ν; η is 0 or 1.

In some embodiments, the ligand is a substituted or unsubstituted crown ether with the formula C in which K represents O and η is 0 or 1. In some embodiments, the ligand is a substituted or unsubstituted crown ether with the formula C in which K represents 8, and η is 0 or 1. In some embodiments, the ligand is a substituted or unsubstituted crown ether with the formula C in which K is Ν and η is 0 or 1. In some embodiments, the ligand is a substituted or unsubstituted crown - an ester of formula C in which K represents P and η is 0 or 1. In some embodiments, the ligand is a substituted or unsubstituted crown ether with formula C in which K is O or 8 and η is 0 or 1 In some embodiments, the ligand is a substituted or unsubstituted crown ether with formula C in which K is O or Ν, and η is 0 or 1. In some embodiments, the ligand is a substituted or unsubstituted crown ether with formula C, which K represents Ν or 8, and η is 0 or 1. In n embodiments where the ligand is a substituted or unsubstituted crown ether with the formula C in which K represents Ν or P, and η is 0 or 1.

Substituted or unsubstituted phosphines.

In some embodiments, the ligand is a substituted or unsubstituted phosphine of formula Ό or an oxide thereof

where K ¹ , K ² and K ³ independently represent H, alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amine, substituted amine, cycloalkyl, substituted cycloalkyl, heterocycloalkyl and substituted heterocycloalkyl.

An example of an oxide of a compound of formula Ό is

where K ¹ , K ² and K ³ independently represent H, alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amine, substituted amine, cycloalkyl, substituted cycloalkyl, heterocycloalkyl and substituted heterocycloalkyl.

In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are alkyl and substituted alkyl. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are alkyl and substituted alkyl, wherein the substituted alkyl is substituted with a group selected from an alkoxy group, a substituted alkoxy group, an amino group, and a substituted amino group. In some embodiments of the compounds of formula Ό or its oxide K ¹ , K ² and K ³

- 15,074,710 independently represent alkyl and substituted alkyl, wherein the substituted alkyl is substituted with a group selected from an alkoxy group and an amino group.

In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently represent an alkoxy group and a substituted alkoxy group. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently represent an alkoxy group and a substituted alkoxy group, the substituted alkoxy group being substituted by a group selected from alkyl, substituted alkyl, amine and substituted amine. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently represent an alkoxy group and a substituted alkoxy group, wherein the substituted alkoxy group is substituted with a group selected from alkyl and amine.

In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently are aryl and substituted aryl. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are aryl and substituted aryl, wherein substituted aryl is substituted with a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amino, and substituted amino. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are aryl and substituted aryl, wherein substituted aryl is substituted with a group selected from alkyl, alkoxy, and amino. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are aryl and substituted aryl, wherein substituted aryl is substituted with a group selected from alkyl and alkoxy.

In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently are heteroaryl and substituted heteroaryl. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently are heteroaryl and substituted heteroaryl, wherein the substituted heteroaryl is substituted by a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amino and substituted amino. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are heteroaryl and substituted heteroaryl, wherein the substituted heteroaryl is substituted with a group selected from alkyl, alkoxy, and amino.

In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently are cycloalkyl or substituted cycloalkyl. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are cycloalkyl or substituted cycloalkyl, wherein the substituted cycloalkyl is substituted with a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amino, and substituted amino. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are cycloalkyl or substituted cycloalkyl, wherein the substituted cycloalkyl is substituted with a group selected from alkyl, alkoxy, and amino.

In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently are heterocycloalkyl and substituted heterocycloalkyl. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ^2, and K ³ independently are heterocycloalkyl and substituted heterocycloalkyl, wherein the substituted heterocycloalkyl is substituted with a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amino, and substituted amino. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently are heterocycloalkyl and substituted heterocycloalkyl, wherein the substituted heterocycloalkyl is substituted with a group selected from an alkyl, alkoxy group and amino group.

In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently represent an amine and a substituted amine. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently represent an amine and a substituted amine, wherein the substituted amine is substituted with a group selected from alkyl, substituted alkyl, alkoxy and substituted alkoxy. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently represent an amine and a substituted amine, wherein the substituted amine is substituted with a group selected from alkyl and alkoxy. In some embodiments, the compounds of formula Ό or its oxide K ¹ , K ² and K ³ independently represent an amine and a substituted amine, wherein the substituted amine is substituted by alkyl.

In some embodiments, the ligand is a substituted or unsubstituted phosphine of formula Ό or an oxide thereof

where K ¹ , K ² and K ³ independently represent H, alkyl; substituted alkyl, substituted by a group selected from alkoxy, substituted alkoxy, amine and substituted amine; aryl; substituted 16,074,710 aryl substituted with a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amine and substituted amine; heteroaryl; substituted heteroaryl substituted with a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amine and substituted amine; amine; a substituted amine substituted with a group selected from alkyl, substituted alkyl, alkoxy and substituted alkoxy; cycloalkyl; substituted cycloalkyl substituted with a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amine and substituted amine; heterocycloalkyl; and substituted heterocycloalkyl substituted with a group selected from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amine and substituted amine.

In some embodiments, the ligand is a substituted or unsubstituted phosphine of formula Ό or its oxide o

where K ¹ , K ² and K ³ independently represent H, alkyl; substituted alkyl substituted with a group selected from alkoxy and amine; aryl; substituted aryl substituted with a group selected from alkyl, alkoxy and amine; heteroaryl; substituted heteroaryl substituted with a group selected from alkyl, alkoxy and amine; amine; a substituted amine substituted with a group selected from alkyl and alkoxy; cycloalkyl; substituted cycloalkyl substituted with a group selected from alkyl, alkoxy and amine; heterocycloalkyl; and substituted heterocycloalkyl substituted with a group selected from alkyl, alkoxy and amine.

Substituted or unsubstituted pyridines.

In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E

where K ¹ and K ² independently represent H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amine, substituted amine, cycloalkyl, substituted cycloalkyl, heterocycloalkyl and substituted heterocycloalkyl.

In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E

where K ¹ and K ² independently represent H, alkyl, substituted alkyl, heteroaryl, substituted heteroaryl, amine and substituted amine.

In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E, in which K ¹ and K ² independently represent H, alkyl and substituted alkyl, wherein the substituted alkyl is substituted by a group selected from an alkoxy group, a substituted alkoxy group, an amine and a substituted amine. In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E, in which K ¹ and K ² independently represent H, alkyl and substituted alkyl, wherein the substituted alkyl is substituted by a group selected from an amine and a substituted amine, wherein the substituted amine is substituted alkyl, heteroaryl or substituted heteroaryl.

In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E, in which K ¹ and K ² independently are heteroaryl and substituted heteroaryl. In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E, in which K ¹ and K ² independently are heteroaryl and substituted heteroaryl substituted with alkyl, alkoxy or amine.

In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E, in which K ¹ and K ² independently represent an amine and a substituted amine. In some embodiments, the ligand is a substituted or unsubstituted pyridine with the formula E, in which K ¹ and K ² independently represent an amine and a substituted amine, wherein the substituted amine is substituted by alkyl, heteroaryl or substituted heteroaryl.

In some embodiments, the ligand is a substituted or unsubstituted pyridine with

- 17,024,710 by formula E

where K ¹ and K ² independently represent H; alkyl; substituted alkyl substituted with a group selected from amine and substituted amine; heteroaryl; substituted heteroaryl substituted with alkyl, alkoxy or amine; and a substituted amine substituted with alkyl, heteroaryl or substituted heteroaryl.

Substituted or unsubstituted dinitriles.

In some embodiments, the ligand is a substituted or unsubstituted dinitrile of formula P

in

G where K represents hydrogen, alkyl or substituted alkyl; η is 0-2; t is 0-3; to is 1-3.

In some embodiments, the ligand is a substituted or unsubstituted dinitrile of formula P, in which K is hydrogen, alkyl or substituted alkyl, substituted with alkoxy or amine; η is 0-1; t is 0-3; and k is 1-3.

In some embodiments, the ligand is a substituted or unsubstituted dinitrile of formula P in which K is hydrogen or alkyl; η is 0-1; t is 0-3; and k is 1-3.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; and metal ion.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; and a metal ion selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and their combinations.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; metal ion; and salt.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; a metal ion selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium , manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combinations thereof; and salt.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; a metal ion selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium , manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combinations thereof; and a salt including sodium chloride, ammonium chloride, sodium sulfate, ammonium sulfate, calcium chloride, or a combination thereof.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; metal ion; and salt

- 18,024,710 including sodium chloride, ammonium chloride, sodium sulfate, ammonium sulfate, calcium chloride, or a combination thereof.

In one aspect, a composition is provided comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; metal ion; salt; and unsaturated or saturated hydrocarbon.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; a metal ion selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium , manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combinations thereof; salt; and unsaturated or saturated hydrocarbon.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; a metal ion selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium , manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combinations thereof; a salt including sodium chloride, ammonium chloride, sodium sulfate, ammonium sulfate, calcium chloride, or a combination thereof; and unsaturated or saturated hydrocarbon.

In one aspect, a composition is provided comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; metal ion; a salt including sodium chloride, ammonium chloride, sodium sulfate, ammonium sulfate, calcium chloride, or a combination thereof; and unsaturated or saturated hydrocarbon.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; metal ion; a salt including sodium chloride, ammonium chloride, sodium sulfate, ammonium sulfate, calcium chloride, or a combination thereof; and an unsaturated or saturated hydrocarbon selected from ethylene, propylene, butylenes, ethane, propane, butane, and combinations thereof.

In one aspect, there is provided a composition comprising an aqueous medium containing a ligand selected from substituted or unsubstituted phosphine, substituted or unsubstituted crown ether, substituted or unsubstituted aliphatic nitrogen-containing compound, substituted or unsubstituted pyridine, substituted or unsubstituted dinitrile, and a combination thereof; a metal ion selected from iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium , manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium, and combinations thereof; and a salt including sodium chloride, ammonium chloride, sodium sulfate, ammonium sulfate, calcium chloride, or a combination thereof; and an unsaturated or saturated hydrocarbon selected from ethylene, propylene, butylenes, ethane, propane, butane, and combinations thereof.

In some embodiments of the methods and devices provided in the text of this description, the ligand is:

sulfonated batocuprin; pyridine;

tris- (2-pyridylmethyl) amine;

glutaronitrile;

iminodiacetonitrile;

malononitrile;

succinic acid nitrile;

tris- (diethylamino) phosphine;

tris- (dimethylamino) phosphine;

tri (2-furyl) phosphine;

tris- (4-methoxyphenyl) phosphine;

bis- (diethylamino) phenylphosphine;

tris- (M, Y-tetramethylene) phosphoric acid triamide;

- 19,024,710 di-tert-butyl - ^^ diisopropylphosphoramidite;

diethylphosphoramidate;

hexamethylphosphoramide;

diethylene triamine;

tris- (2-aminoethyl) amine;

Ν, Ν, Ν ', Ν', Ν '' - pentamethyldiethylene triamine;

15-crown-5;

1,4,8,11-tetrathacyclotetradecane and their salts or stereoisomers.

In some embodiments, there is provided a method of using a ligand, comprising adding a ligand to an anolyte containing a solution of a metal ion, and leading to the appearance of one or more properties, including, but not limited to, the increased reactivity of the metal ion with respect to an unsaturated hydrocarbon, saturated hydrocarbon or hydrogen gas; increased selectivity of the metal ion with respect to the halogenation of an unsaturated or saturated hydrocarbon; increased halogen transfer from the metal ion to an unsaturated hydrocarbon, saturated hydrocarbon or hydrogen gas; reduced redox potential of the electrochemical cell; increased solubility of the metal ion in the aquatic environment; reduced transfer of the metal ion through the membrane into the catholyte of the electrochemical cell; reduced corrosion of the electrochemical cell and / or reactor; increased separation of the metal ion from the acidic solution after reaction with hydrogen gas; increased separation of the metal ion from the halogenated hydrocarbon solution; and their combination.

In some embodiments, a method is provided comprising increasing the efficiency of an electrochemical cell, wherein the electrochemical cell comprises an anode in contact with an anolyte containing a metal ion, wherein the anode oxidizes the metal ion from a lower oxidation state to a higher oxidation state. In some embodiments, efficiency is related to the voltage applied to the electrochemical cell.

The term alkenyl, as used herein, refers to a linear or branched hydrocarbon residue comprising from 2 to 10 carbon atoms, and in some embodiments from 2 to 6 carbon atoms or from 2 to 4 carbon atoms, and having at least one unsaturated vinyl group (> C = C <). For example, ethenyl, propenyl, 1,3-butadienyl and the like.

The term alkoxy used in the text of this description refers to the group-O-alkyl, where the term alkyl is defined below in this description. The alkoxy group includes, by way of example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy and n-pentoxy.

The term alkyl, as used herein, refers to monovalent saturated aliphatic hydrocarbon groups comprising from 1 to 10 carbon atoms and, in some embodiments, from 1 to 6 carbon atoms. The term Cx-C _in alkyl refers to alkyl groups comprising x to y carbon atoms. This term includes, by way of example, linear and branched hydrocarbon groups such as methyl (CH ₃ -), ethyl (CH ₃ CH ₂ -), n-propyl (CH ₃ CH ₂ CH ₂ -), isopropyl ((CH ₃ ) ₂ CH-), n-butyl (CH ₃ CH ₂ CH ₂ CH ₂ -), isobutyl ((CH ₃ ) ₂ CHCH ₂ -), sec-butyl ((CH ₃ ) (CH ₃ CH ₂ ) CH-) , tert-butyl ((CH3) 3C-), n-pentyl (CH3CH2CH2CH2CH2-) and neopentyl ((CH3) 3CCH2-).

The term amino group or amine, as used in the text of this description, refers to the group Ν4 ₂ .

The term aryl, as used in the text of this description, refers to an aromatic group of 6-14 carbon atoms that does not contain heteroatoms in the ring and has a single ring (e.g. phenyl) or several fused (combined) rings (e.g. naphthyl or antryl).

The term cycloalkyl, as used in the text of this description, refers to a saturated or partially saturated cyclic group of 3-14 carbon atoms, not containing heteroatoms in the ring and having a single ring or several rings, including condensed, bridged and spiro-ring systems. Examples of cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl and cyclohexenyl

The term halo or halogen used in the text of this description refers to fluorine, chlorine, bromine and iodine.

The term heteroaryl, used in the text of this description, refers to an aromatic group containing 1-6 heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, and includes systems with a single ring (e.g., furanyl) and with multiple rings (e.g., benzimidazol-2-yl and benzimidazol-6-yl). Heteroaryl includes, but is not limited to, pyridyl, furanyl, thienyl, thiazolyl, isothiazolyl, triazolyl, imidazolyl, isoxazolyl, pyrrolyl, pyrazolyl, pyridazinyl, pyrimidinyl, benzofuranyl, benzodiisolazolazolazinazolazinazole-azolazolazinazole-azolazolazinazolazole , tetrahydroquinolinyl, isoquinolyl, quinazolinonyl, benzimidazolyl, benzisoxazolyl or benzothienyl.

The term heterocycloalkyl, as used herein, refers to saturated

- 20,047,710 or a partially saturated cyclic group comprising from 1 to 5 heteroatoms selected from the group consisting of nitrogen, sulfur or oxygen, and includes systems with one ring or with several rings, including condensed, bridged and spiro-ring systems. Heterocycloalkyl includes, but is not limited to, tetrahydropyranyl, piperidinyl, Ν methylpiperidin-3-yl, piperazinyl, Ν-methylpyrrolidin-3-yl, 3-pyrrolidinyl, 2-pyrrolidon-1-yl, morpholinyl and pyrrolidinyl.

The term substituted alkoxy group, as used herein, refers to the group —O-substituted alkyl, in which the term substituted alkyl is defined below in the text of this description.

The term substituted alkyl, as used in the text of this description, refers to an alkyl group comprising from 1 to 5, and in some embodiments from 1 to 3, or from 1 to 2 substituents selected from the group consisting of alkenyl, halogen, —OH, - COOH, an amino group, a substituted amino group, and these substituents are defined in the text of this description.

The term “substituted amino group” or “substituted amine” as used herein refers to the group —ΝΚ ¹⁰ ΝΚ ¹¹ , where K ¹⁰ and K ^{11 are} independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl.

The term substituted aryl, as used in the text of this description, refers to an aryl group which is substituted by 1-8, and in some embodiments 1-5, 1-3 or 1-2 by substituents selected from the group consisting of alkyl, substituted alkyl, alkoxy substituted alkoxygroup, amine, substituted amine, alkenyl, halogen, —OH and —COOH, and these substituents are defined in the text of this description.

The term substituted cycloalkyl, as used herein, refers to a cycloalkyl group, as defined herein, having from 1 to 8 or from 1 to 5 or, in some embodiments, from 1 to 3 substituents selected from the group consisting of from alkyl, substituted alkyl, alkoxy, substituted alkoxy, amine, substituted amine, alkenyl, halogen, —OH and —COOH, the substituents being defined in the text of this description.

The term substituted heteroaryl, as used throughout this specification, refers to heteroaryl groups that are substituted with 1-5 or 1-3 or 1-2 substituents selected from the group consisting of substituents defined for substituted aryl.

The term substituted heterocycloalkyl, as used herein, refers to cyclic groups, as defined herein, which are substituted with 1 to 5 or, in some embodiments, 1 to 3 substituents as defined for substituted cycloalkyl.

It should be understood that in all the substituted groups defined above, this concept is not intended to include polymers obtained by the determination of substituents which themselves contain substituents (for example, substituted aryl having as its substituent a substituted aryl group which itself is substituted by a substituted aryl group, etc.). In such cases, the maximum number of such substituents is three. Similarly, it should be understood that the above definitions are not intended to include unacceptable substitution cases (e.g. methyl substituted with 5 chlorine atoms). Such unacceptable substitution cases are well known in the art.

In some embodiments, the concentration of the ligand in the electrochemical cell depends on the concentration of a metal ion in a lower and / or higher oxidation state. In some embodiments, the concentration of the ligand is from 0.25 to 5 M; or from 0.25 to 4 M; or from 0.25 to 3 M; or from 0.5 to 5 M; or from 0.5 to 4 M; or from 0.5 to 3 M; or from 0.5 to 2.5 M; or from 0.5 to 2 M; or from 0.5 to 1.5 M; or from 0.5 to 1 M; or from 1 to 2 M; or from 1.5 to 2.5 M; or from 1.5 to 2 M.

In some embodiments, the ratio of ligand concentration to Cu (1) ion concentration is from 1: 1 to 4: 1; or from 1: 1 to 3: 1; or from 1: 1 to 2: 1; or equal to 1: 1; or 2: 1; or 3: 1; or 4: 1.

In some embodiments, the solution used in the catalytic reaction, i.e. the reaction of a metal ion in a higher oxidation state with an unsaturated or saturated hydrocarbon, and the solution used in the electrochemical reaction contain a concentration of a metal ion in a higher oxidation state, e.g. Cu (11), from 4.5 to 7 M, concentration a metal ion in a lower oxidation state, for example Cu (1), from 0.25 to 1.5 M, and a ligand concentration of from 0.25 to 6 M. In some embodiments, the concentration of sodium chloride in solution may affect the solubility of the ligand and / or metal ion, yield and selectivity catalytic reaction, and / or to the efficiency of the electrochemical cell. Accordingly, in some embodiments, the concentration of sodium chloride in the solution is from 1 to 3 M. In some embodiments, the solution used in the catalytic reaction, i.e. in the reaction of a metal ion in a higher oxidation state with an unsaturated or saturated hydrocarbon, and the solution used in the electrochemical reaction contain a concentration of a metal ion in a higher oxidation state, for example Cu (11), from 4.5 to 7 M, the concentration of the metal ion in a lower oxidation state, for example Cu (1), from 0.25 to 1.5 M, the ligand concentration from 0.25 to 6 M and the concentration of sodium chloride from 1 to 3 M.

- 21,024,710

Electrochemical methods and devices.

In one aspect, methods are provided comprising contacting the anode with a metal ion located in the anolyte of the anode compartment; transfer of a metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; and bringing the cathode into contact with the catholyte in the cathode compartment. In one aspect, methods are provided comprising contacting the anode with a metal ion in the anolyte in the anode compartment; transfer of a metal ion from a lower oxidation state to a higher oxidation state in the anode compartment; bringing the cathode into contact with the catholyte in the cathode compartment; and obtaining alkali, water and / or hydrogen gas in the cathode compartment. In one aspect, methods are provided comprising contacting the anode with a metal ion in the anolyte in the anode compartment; transfer of a metal ion from a lower oxidation state to a higher oxidation state in the anode compartment; and processing the metal ion, which is in a higher oxidation state, with an unsaturated or saturated hydrocarbon. In some embodiments, treatment of a metal of a higher oxidation state with an unsaturated or saturated hydrocarbon results in the formation of halogenated hydrocarbons. In some embodiments, the treatment of a metal ion at a higher oxidation state with an unsaturated or saturated hydrocarbon is carried out inside the anode compartment. In some embodiments, the treatment of a metal ion at a higher oxidation state with an unsaturated or saturated hydrocarbon is carried out outside the anode compartment. In some embodiments, the cathode is an oxygen depolarization cathode.

Some embodiments of electrochemical cells are illustrated in the drawings and described herein. It should be understood that the drawings are for illustrative purposes only, and changes in reagents and hardware design are also included in the scope of this invention. All electrochemical methods and devices described in this text do not produce gaseous chlorine, as is the case in plants for the production of chlorine and alkali. All devices and methods associated with the halogenation or sulfonation of an unsaturated or saturated hydrocarbon do not use gaseous oxygen in the catalytic reactor.

In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; transfer or oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; and the formation of alkali, water and / or hydrogen gas at the cathode. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; the formation of alkali, water and / or hydrogen gas at the cathode; and bringing an anolyte containing a higher oxidation metal ion into contact with an unsaturated and / or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing an anolyte containing a higher oxidation metal ion into contact with hydrogen gas to obtain an acid , or a combination of both of these processes.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode compartment configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a cathode in contact with the catholyte. In another aspect, devices are provided comprising an anode compartment, including an anode in contact with a metal ion in the anolyte, the anode compartment configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a cathode in contact with the catholyte, wherein the cathode compartment is configured to produce alkali, water and / or hydrogen gas. In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a cathode in contact with the catholyte, wherein the cathode is configured to produce alkali, water and / or hydrogen gas in catholyte; and a reactor operably connected to the anode compartment and configured to contact an anolyte containing a metal ion of a higher oxidation state with an unsaturated and / or saturated hydrocarbon and / or gaseous hydrogen to produce a halogenated hydrocarbon or acid, respectively. In another aspect, devices are provided comprising an anode compartment, including an anode in contact with a metal ion in the anolyte, the anode compartment configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and an unsaturated and / or saturated hydrocarbon feed system configured to supply an unsaturated and / or saturated hydrocarbon to the anode compartment; however, the anode compartment is also configured to convert an unsaturated and / or saturated hydrocarbon into a halogenated hydrocarbon.

As illustrated in FIG. 1A, the electrochemical device 100A includes an anode compartment with an anode in contact with the anolyte, where the anolyte contains metal ions of a lower oxidation state (represented as M ⁺ ), which are converted to a higher degree of metal ions on the anode

- 22,024,710 oxidation (represented as M ^{n +} ). The metal ion may be in the form of sulfate, chloride, bromide or iodide.

Used in the text of this description, the lower oxidation state, presented in M ^b + as b +, includes a lower metal oxidation state. For example, a lower oxidation state of a metal ion may be 1+, 2+, 3+, 4+, or 5+. Used in the text of this description, a higher oxidation state, presented in M ⁿ + as H +, includes a higher oxidation state of the metal. For example, a higher oxidation state of a metal ion may be 2+, 3+, 4+, 5+, or 6+.

The electrons generated at the anode are used to conduct the reaction at the cathode. The cathodic reaction may be any reaction known in the art. The anode and cathode compartments can be separated by an ion exchange membrane (IOM), which can allow the passage of ions, for example, in some embodiments, sodium ions (not limited to) into the catholyte, if the anolyte is sodium chloride or sodium sulfate, etc., containing metal halide. Some reactions that can take place at the cathode include, but are not limited to, the reaction of water to form hydroxide ions and hydrogen gas, the reaction of gaseous oxygen and water to form hydroxide ions, the reduction of HC1 to form hydrogen gas, or the reaction of HC1 and oxygen gas with the formation of water.

As illustrated in FIG. 1B, the electrochemical device 100B includes a cathode compartment with a cathode in contact with a catholyte that produces hydroxide ions in catholyte. The electrochemical device 100B also includes an anode compartment with an anode in contact with the anolyte; while the anolyte contains metal ions in a lower oxidation state (represented as M ^b +), which are converted on the anode into metal ions in a higher oxidation state (represented as M ^{n +} ). The electrons generated at the anode are used to conduct the reaction at the cathode. The anode and cathode compartments are separated by an ion-exchange membrane (IOM), which allows sodium ions to pass into the catholyte if the anolyte is sodium chloride, sodium bromide, sodium iodide, sodium sulfate, ammonium chloride, etc., or an equivalent solution containing metal halide . In some embodiments, the ion exchange membrane allows anions to pass into the anolyte, for example, but not limited to chloride ions, bromide ions, iodide ions or sulfate ions, if the catholyte is, for example, sodium chloride, sodium bromide, sodium iodide or sulfate sodium, or equivalent solution. Sodium ions combine with hydroxide ions in catholyte to form sodium hydroxide. Anions combine with metal ions to form a metal halide or sulfate. It should be understood that the cathode on which the hydroxide is formed, as shown in FIG. 1B is for illustrative purposes only; and for such devices other cathodes are equally applicable, for example, a cathode that restores HC1 to form hydrogen gas, or a cathode on which both HC1 and oxygen gas react with the formation of water. Such cathodes are also described in this text.

In some embodiments, the electrochemical devices of this invention include one or more ion exchange membranes. Accordingly, in some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; the formation of alkali, water and / or hydrogen gas at the cathode; and separating the cathode and the anode of the at least one ion exchange membrane. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; the formation of alkali, water and / or hydrogen gas at the cathode; separation of the cathode and anode by at least one ion-exchange membrane; and bringing the anolyte containing the metal ion in a higher oxidation state into contact with an unsaturated or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing the anolyte containing the metal ion in a higher oxidation state into contact with hydrogen gas to obtain an acid, or a combination of both of these processes. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; a cathode compartment including a cathode in contact with the catholyte, wherein the cathode is configured to produce alkali, water and / or hydrogen gas; and at least one ion exchange membrane separating the cathode and anode. In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion located in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; the cathode compartment, including the cathode in contact with the catholyte, while the cathode is made with

- 23,024,710 the possibility of obtaining alkali, water and / or gaseous hydrogen; at least one ion exchange membrane separating the cathode and anode; and a reactor operably connected to the anode compartment and configured to bring an anolyte containing a metal ion of a higher oxidation state into contact with an unsaturated and / or saturated hydrocarbon and / or gaseous hydrogen to produce a halogenated hydrocarbon and acid, respectively. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

As illustrated in FIG. 2, the electrochemical device 200 includes a cathode in contact with the catholyte and an anode in contact with the anolyte. The cathode forms hydroxide ions in the catholyte, and the anode transfers metal ions from a lower oxidation state (M ⁺ ) to a higher oxidation state (M ^H +). The anode and cathode are separated by an anion exchange membrane (AOM) and a cation exchange membrane (COM). A third electrolyte (e.g., sodium chloride, sodium bromide, sodium iodide, sodium sulfate, ammonium chloride, or a combination thereof, or an equivalent solution) is located between the AOM and KOM. Sodium ions from the third electrolyte pass through KOM with the formation of sodium hydroxide in the cathode compartment; and halides, for example, chloride, bromide or iodide ions, or sulfate ions, pass from the third electrolyte through AOM to form a solution of a metal halide or metal sulfate in the anode compartment. Then, the metal halide or metal sulfate obtained in the anolyte is fed to the reactor for reaction with hydrogen gas or an unsaturated or saturated hydrocarbon to obtain hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrogen bromide, hydrogen iodide or hydrogen iodide acid and / or halogenated hydrocarbons, respectively. The third electrolyte, after ion transfer, can be taken from the middle chamber as an ion-depleted solution. For example, in some embodiments, if the third electrolyte is a sodium chloride solution, then after transferring the sodium ions to the catholyte and transferring the chloride ions to the anolyte, a depleted sodium chloride solution can be taken from the middle chamber. The depleted solution can be used for commercial purposes, or it can be transferred to the anode and / or cathode compartment as an electrolyte or concentrated for reuse as a third electrolyte. In some embodiments, depleted saline may be useful for producing demineralized water. It should be understood that the cathode on which the hydroxide is formed, as shown in FIG. 2 is shown for illustrative purposes only, and similarly, other cathodes can be used in these devices, for example, a cathode reducing HC1 to produce hydrogen gas, or a cathode to which both HC1 and oxygen gas react to produce water; such cathodes are also described in this text.

In some embodiments, the two ion exchange membranes shown in FIG. 2 can be replaced with a single ion exchange membrane, as shown in FIG. 1A or 1B. In some embodiments, the ion exchange membrane is an anion exchange membrane, as illustrated in FIG. 3A. In such embodiments, the catholyte may be sodium halide, sodium sulfate or an equivalent solution, and the AOM is such that it allows the anions to transfer to the anolyte, but prevents the transfer of metal ions from the anolyte to the catholyte. In some embodiments, the ion exchange membrane is a cation exchange membrane, as illustrated in FIG. 3B. In such embodiments, the anolyte may be sodium halide, sodium sulfate or an equivalent solution containing a metal halide solution or an equivalent solution, and KOM is such that it allows sodium ions to transfer to the catholyte, but prevents the transfer of metal ions from the anolyte to catholyte. In some embodiments, the use of one ion-exchange membrane instead of two ion-exchange membranes can reduce the resistance created by numerous IOMs, and can contribute to the electrochemical reaction at lower voltages. The text of this description provides some examples of suitable anion exchange membranes.

In some embodiments, the cathode used in the electrochemical devices of this invention is a cathode on which hydrogen gas is generated. Accordingly, in some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; the formation of alkali and hydrogen gas at the cathode. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; the formation of alkali and hydrogen gas at the cathode; and bringing the anolyte containing the metal ion in a higher oxidation state into contact with an unsaturated or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing the anolyte containing the metal ion in a higher oxidation state into contact with hydrogen gas to obtain an acid, or a combination of both of these processes. In some embodiments, the method further comprises separating the cathode and the anode of the at least one ion exchange membrane. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof. In certain 2424710 embodiments, the method cited above includes an anode on which no gas is generated. In some embodiments, the method includes an anode that does not use gas.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion located in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a cathode in contact with the catholyte, wherein the cathode is configured to produce alkali and hydrogen gas. In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion located in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a cathode in contact with the catholyte, wherein the cathode is configured to produce alkali and hydrogen gas; and a reactor operably connected to the anode compartment and configured to contact an anolyte containing a metal ion of a higher oxidation state with an unsaturated or saturated hydrocarbon and / or gaseous hydrogen to produce a halogenated hydrocarbon and acid, respectively. In some embodiments, the device is configured such that no gas is formed at the anode. In some embodiments, the device is designed such that gas is not used at the anode. In some embodiments, the device further includes at least one ion-exchange membrane separating the cathode and anode. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

For example, as illustrated in FIG. 4A, the electrochemical device 400 includes a cathode in contact with catholyte 401, a hydroxide being formed in the catholyte. The device 400 also includes an anode in contact with anolyte 402, which converts metal ions in a lower oxidation state (M ^{b +} ) into metal ions in a higher oxidation state (M ^H +). The following are the reactions that occur at the cathode and at the anode:

H ₂ O + e -> 1 / 2H ₂ + OH '(cathode)

M ¹⁺ -> M ^{n +} + xe (anode, where x = 1-3)

For example, Re ²⁺ -> Re ³⁺ + e (anode)

Cr ² * -> Cr ³⁴ + e '(anode)

Зп ²⁺ - »Зп ⁴⁺ + 2е (anode)

CuG -> Cu ²⁴ + e (anode)

As illustrated in FIG. 4A, the electrochemical device 400 includes a cathode on which hydroxide ions and hydrogen gas are formed. Hydrogen gas can be released or trapped and stored for commercial purposes. In some embodiments, the hydrogen evolved at the cathode can be halogenated and sulfonated (including sulfated) with a metal halide or metal sulfate formed in the anolyte to produce hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydrogen iodide acid or sulfuric acid. Such a reaction is described in detail in this text. M ^H + formed at the anode combines with chloride ions to form a metal chloride at a higher oxidation state, for example, but not limited to FeCl ₃ , Cr Cl ₃ , ₈ ClCl ₄ or CuCl ₂ , etc. The hydroxide ion formed at the cathode combines with sodium ions to form sodium hydroxide.

It should be understood that chloride ions in this application are for illustrative purposes only, and that other equivalent ions, for example (but not limited to) sulfate, bromide or iodide, are also included in the scope of this invention and may lead to the formation of the corresponding metal halide or sulfate metal in anolyte. It should also be understood that MC1 _p , shown in the drawings here by way of illustration, is a mixture of a metal ion in a lower oxidation state and a metal ion in a higher oxidation state. The integer n in MC1 _n simply represents a metal ion with a lower oxidation state and a higher oxidation state and can be from 1 to 5 or more, depending on the metal ion. For example, in some embodiments, where the metal ion is copper, MC1 _n may be a mixture of CuCl and CuCl ₂ . This mixture of copper ions in the anolyte can then be brought into contact with hydrogen gas, an unsaturated hydrocarbon and / or saturated hydrocarbon to produce the corresponding products.

In some embodiments, the cathode used in the electrochemical devices of this invention is a cathode producing hydrogen gas on which alkali does not form. Accordingly, in some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; obtaining hydrogen gas at the cathode. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a more

- 25,024,710 highly oxidized; bringing the cathode into contact with the catholyte in the cathode compartment; obtaining hydrogen gas at the cathode; and bringing the anolyte containing the metal ion in a higher oxidation state into contact with an unsaturated or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing the anolyte containing the metal ion in a higher oxidation state into contact with hydrogen gas to obtain an acid, or a combination of both of these processes. In some embodiments, the method further comprises separating the cathode and the anode of the at least one ion exchange membrane. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof. In some embodiments, the method cited above includes an anode on which no gas is generated. In some embodiments, the method includes an anode that does not use gas.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a cathode in contact with the catholyte, wherein the cathode is configured to produce hydrogen gas. In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a cathode in contact with the catholyte, wherein the cathode is configured to produce hydrogen gas; and a reactor operably connected to the anode compartment and configured to bring an anolyte containing a metal ion of a higher oxidation state into contact with an unsaturated or saturated hydrocarbon and / or gaseous hydrogen to produce a halogenated hydrocarbon and acid, respectively. In some embodiments, the device is configured such that no gas forms at the anode. In some embodiments, the device is designed such that no gas is used at the anode. In some embodiments, the device further includes at least one ion-exchange membrane separating the cathode and anode. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

For example, as illustrated in FIG. 4B, the electrochemical device 400 includes a cathode in contact with catholyte 401, the hydrochloric acid supplied to the catholyte being converted into catholyte in gaseous hydrogen. The device 400 also includes an anode in contact with anolyte 402, which converts metal ions of a lower oxidation state (M ^{b +} ) into metal ions of a higher oxidation state (M ⁿ +). The following are the reactions that occur at the cathode and at the anode:

2Н * + 2е '-> Н ₂ (cathode)

M ¹ * -> M ⁿ * + xe '(anode, where x = 1-3)

For example, Re ² * -> Re ³ * + e '(anode)

Cr ² * -> Cr ³ * + e '(anode)

5p ² * -> 5p ⁴ * + 2e '(anode)

Cu * - »Cu ² * + e (anode)

As illustrated in FIG. 4B, an electrochemical device 400 includes a cathode on which hydrogen gas is generated. Hydrogen gas can be released or trapped and stored for commercial purposes. In some embodiments, the hydrogen evolved at the cathode can be halogenated or sulfonated (including sulfated) with a metal halide or metal sulfate formed in the anolyte to produce hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, iodide -hydrogen acid or sulfuric acid. Such a reaction is described in detail in this text. M ⁿ + formed at the anode combines with chloride ions to form a metal chloride at a higher oxidation state, for example, but not limited to FeCl ₃ , Cr Cl ₃ , ₈ ClCl ₄ or CuCl ₂ , etc. The hydroxide ion formed at the cathode combines with sodium ions to form sodium hydroxide.

It should be understood that one AOM shown in FIG. 4B is provided for illustrative purposes only, and it is possible to construct a device that includes KOM, with HC1 being supplied to the anolyte, and hydrogen ions passing through the KOM to the catholyte. In some embodiments, the device illustrated in FIG. 4B may contain both AOM and KOM, and the middle chamber contains chloride salt. It should also be understood that MC1 _p , shown in the drawings in the text of this description, is a mixture of a metal ion in a lower oxidation state and a metal ion in a higher oxidation state. The integer η in MC1 _n simply represents a metal ion in a lower oxidation state and a higher oxidation state and may be 1-5 or more, depending on the metal ion. For example, in some embodiments, where the metal ion is copper, MC1 _n may be a mixture of CuCl and CuCl ₂ . This mixture of copper ions in the anolyte can then be brought into contact with hydrogen gas, an unsaturated hydrocarbon and / or saturated hydrocarbon to obtain the corresponding products.

- 26,024,710

In some embodiments, the cathode in the electrochemical devices of this invention may be a gas diffusion cathode. In some embodiments, the cathode in the electrochemical devices of this invention may be a gas diffusion cathode on which alkali is formed. In some embodiments, methods are provided that include contacting the anode with a metal ion located in the anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and bringing the gas diffusion cathode into contact with the catholyte. In some embodiments, the gas diffusion cathode is an oxygen depolarization (QCD) cathode. In some embodiments, the method comprises alkali formation on KKD. In some embodiments, methods are provided that include contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and bringing the cathode into contact with the catholyte, wherein the cathode is an oxygen depolarization cathode that reduces oxygen and water to hydroxide ions. In some embodiments, methods are provided that include contacting the anode with a metal ion in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the gas diffusion cathode into contact with the catholyte in the cathode compartment; alkali formation at the cathode; and bringing an anolyte containing a higher oxidation metal ion into contact with an unsaturated and / or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing an anolyte containing a higher oxidation metal ion into contact with hydrogen gas to obtain an acid , or a combination of both of these processes. In some embodiments, no gas is generated at the gas diffusion cathode. In some embodiments, the method includes an anode on which no gas is generated. In some embodiments, the method includes an anode that does not use gas. In some embodiments, the method further comprises separating the cathode and the anode of the at least one ion exchange membrane. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in an anolyte, the anode configured to convert or oxidize a metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a gas diffusion cathode in contact with the catholyte, wherein the cathode is configured to produce alkali. In some embodiments, the gas diffusion cathode is an oxygen depolarization (QCD) cathode. In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a gas diffusion cathode in contact with the catholyte, wherein the cathode is configured to produce alkali; and a reactor operably connected to the anode compartment and configured to contact an anolyte containing a metal ion of a higher oxidation state with an unsaturated and / or saturated hydrocarbon and / or gaseous hydrogen to produce a halogenated hydrocarbon and acid, respectively. In some embodiments, the device is configured such that no gas is generated at the gas diffusion cathode. In some embodiments, the device is configured such that no gas forms at the anode. In some embodiments, the device is designed such that no gas is used at the anode. In some embodiments, the device further includes at least one ion-exchange membrane separating the cathode and anode. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

The terms gas diffusion cathode or gas diffusion electrode or other equivalents used in the text of this description include any electrode on which a gas reaction can occur with the formation of ionic particles. In some embodiments, the gas diffusion cathode used in the text of this description is a cathode with oxygen depolarization (QCD). Such a gas diffusion cathode can be called a gas diffusion electrode, an oxygen consuming cathode, an oxygen reducing cathode, a breathing oxygen cathode, an oxygen depolarization cathode, and the like.

In some embodiments, as illustrated in FIG. 5A, the combination of a gas diffusion cathode (e.g., QCD) and an anode in an electrochemical cell can lead to alkali formation in the cathode compartment. In some embodiments, the electrochemical device 500 includes a gas diffusion cathode in contact with catholyte 501 and an anode in contact with anolyte 502. The anode and cathode are separated by an anion exchange membrane (AOM) and a cation exchange membrane (COM). A third electrolyte (e.g., sodium halide or sodium sulfate) is located between AOM and KOM. The following are the reactions that can occur at the anode and cathode:

- 27,024,710

Н ₂ 0 + 1 / 2О2 + 2е - »20Н '(cathode)

Μ ^{ί +} -> M ^{n +} + xe '(anode, where x = 1-3)

For example, 2Re ² * Re ³ * + 2e '(anode)

2CA - »2Cg ³⁺ + 2e (anode)

5p ²⁺ -> 5p ⁺⁺ + 2e '(anode)

2Си ⁺ -> 2Си ²⁺ + 2е '(anode)

M ⁿ + formed at the anode is combined with chloride ions to form metal chloride MC1 _R, for example, without limitation, ReS1 _3, SGS1 _{3, 4} or §pS1 SiS1 _2, etc. The hydroxide ion formed at the cathode reacts with sodium ions to form sodium hydroxide. The oxygen at the cathode may be from atmospheric air or from any commercially available source of oxygen.

Methods and devices comprising a gas diffusion cathode or QCD, as described herein and illustrated in FIG. 5A can lead to lower voltages compared to methods and devices that include a cathode on which hydrogen gas is generated (as illustrated in FIG. 4A). Reduced voltage, in turn, can lead to less electricity consumption and less carbon dioxide emissions from electricity production. This can lead to the production of greener chemicals, such as sodium hydroxide, halogenated hydrocarbons and / or acids, which are obtained using the efficient and energy-saving methods and devices of this invention. In some embodiments, an electrochemical cell with

KKD gives a theoretical decrease in voltage of more than 0.5 V, or more than 1 V, or more than 1.5 V, or from 0.5 to 1.5 V compared to an electrochemical cell without QCD or compared to an electrochemical cell with a cathode, by which emits hydrogen gas. In some embodiments, stress reduction is achieved at a catholyte pH of from 7 to 15, or from 7 to 14, or from 6 to 12, or from 7 to 12, or from 7 to 10.

The total voltage on the cell can be determined using a combination of Nernst equations for each of the half-reactions occurring in the cell

Е = Е ° - КТ 1п (О) / пР where Е ° - standard recovery potential;

K is the universal gas constant (8.314 J / (mol-K));

T is the absolute temperature;

n is the number of electrons participating in a given half-reaction;

P - Faraday constant (96485 J / (V-mol));

O is the reaction coefficient; so that

E _o6sh - Eanod - Ekatode

If a metal in a lower oxidation state is oxidized at the anode to a metal in a higher oxidation state as follows:

E _anode , depending on the change in the concentration of copper ions (11), can be from 0.159 to 0.75 V.

If water is reduced at the cathode to hydroxide ions and hydrogen gas (as illustrated in FIG. 4A) as follows:

E _cathode = -0.059 pH _k , where pH _k is the pH of catholyte = 14.

Ekatode = -0.83 V.

Thus, E _Tot ranges from 0.989 to 1.53 V, depending on the concentration of copper ions in the anolyte.

If water is reduced to hydroxide ions in a CDC (as illustrated in FIG. 5A) as follows:

Todd E _ka = 1.224 - 0.059 RNA, which RNA = 14;

E = 0 4 V cathode then E _total is from -0.241 to 0.3 V, depending on the concentration of copper ions in the anolyte. Thus, the use of QCD in the cathode compartment gives a theoretical decrease in potential in the cathode compartment or a theoretical decrease in voltage in the cell of approximately 1.5 V or from 0.5 to 2V or from 0.5 to 1.5 V or from 1 to 1 , 5 V, in comparison with an electrochemical cell without QCD or in comparison with an electrochemical cell with a cathode on which hydrogen gas is formed.

Accordingly, in some embodiments methods are provided that include casting

- 28,024,710 anodes in contact with a metal ion in the anolyte; bringing the cathode with oxygen depolarization into contact with the catholyte; application of voltage to the anode and cathode; alkali formation at the cathode; the conversion of a metal ion from a lower oxidation state to a higher oxidation state at the anode; and a decrease in voltage of more than 0.5 V or from 0.5 to 1.5 V compared to the cathode on which hydrogen gas is formed, or compared to a cell without QCD. In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment, including a cathode with oxygen depolarization in contact with the catholyte, while the cathode is made with the possibility of alkali; however, the device provides a voltage reduction of more than 0.5 V or from 0.5 to 1.5 V compared to a device with a cathode on which hydrogen gas is generated, or compared to a device without QCD. In some embodiments, the voltage reduction is a theoretical voltage reduction, which may vary depending on the ohmic resistance of the cell.

While the methods and devices containing a gas diffusion cathode or QCD, lead to a decrease in voltage compared with methods and devices containing a cathode on which hydrogen gas is formed, both devices according to this invention, i.e. devices containing QCD and devices containing a cathode on which hydrogen gas is generated provide a significant reduction in voltage compared to a conventional chlor-alkali system known in the art. In turn, lowering the voltage can lead to lower energy consumption and lower emissions of carbon dioxide when generating electricity. This can lead to the production of greener chemicals, for example, sodium hydroxide, halogenated hydrocarbons and / or acids, which are obtained using the efficient and energy-saving methods and devices of this invention. For example, voltage reduction is beneficial in the production of halogenated hydrocarbons, for example, EDC, which is usually obtained by reacting ethylene with chlorine gas, obtained using a chlor-alkali process that requires high voltage. In some embodiments, the electrochemical device of this invention (cells with two or three compartments, with a cathode on which hydrogen gas is formed, or KKD) give a theoretical decrease in voltage of more than 0.5 V, or more than 1 V, or more than 1.5 V, and from 0.5 to 3V, compared with the chlor-alkali process. In some embodiments, this stress reduction is achieved at a catholyte pH of from 7 to 15, or from 7 to 14, or from 6 to 12, or from 7 to 12, or from 7 to 10.

For example, the theoretical value of the E _anode in the chlor-alkali process is approximately 1.36 V, with the following reaction:

The theoretical value of the E _cathode in the chlor-alkali process is approximately -0.83 V (at pH> 14), with the following reaction:

Thus, the theoretical value of E _total for the chlor-alkali process is 2.19 V. The theoretical value of E _total for the cathode on which hydrogen gas is formed in the device according to this invention is from 0.989 to 1.53 V, and E _total for QCD in the device according to this invention is from -0.241 to 0.3 V, depending on the concentration of copper ions in the anolyte. Thus, the electrochemical devices of this invention provide a theoretical decrease in voltage in the cathode compartment or a theoretical decrease in voltage in the cell by more than 3 V, or more than 2 V, or from 0.5 to 2.5 V, or from 0.5 up to 2.0 V, or from 0.5 to 1.5 V, or from 0.5 to 1.0, or from 1 to 1.5 V, or from 1 to 2 V, or from 1 to 2.5 In, or from 1.5 to 2.5 V, compared with the chlor-alkali system.

In some embodiments, the electrochemical cell may be conditioned with a first electrolyte, and may be operated with a second electrolyte. For example, in some embodiments, the electrochemical cell and AOM, KOM or a combination thereof are conditioned with sodium sulfate as an electrolyte, and after voltage stabilization with sodium sulfate, the cell can work with sodium chloride as an electrolyte. An illustrative example of such stabilization of an electrochemical cell is given here in Example 13. Accordingly, in some embodiments, methods are provided that include contacting the anode with the first anolyte in the anode compartment; bringing the cathode into contact with the catholyte in the cathode compartment; separation of the cathode and anode by at least one ion-exchange membrane; conditioning the ion exchange membrane with the first anolyte in the anode compartment; bringing the anode into contact with a second anolyte containing a metal ion; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and obtaining alkali, water and / or hydrogen gas at the cathode. In some embodiments, the first anolyte is sodium sulfate and the second anolyte is sodium chloride. In some embodiments, the method further includes contacting the second anolyte containing the metal ion with a higher oxidation state to contact an unsaturated and / or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing the second anolyte containing the metal ion with a higher oxidation state into contact with hydrogen gas to get acid, or a combination

- 29,024,710 of both of these processes. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

In some embodiments, the cathode in the electrochemical devices of this invention may be a gas diffusion cathode that reacts with HC1 or gaseous oxygen to produce water. In some embodiments, methods are provided that include contacting the anode with a metal ion in the anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and bringing the gas diffusion cathode into contact with the catholyte. In some embodiments, the gas diffusion cathode is an oxygen depolarization (QCD) cathode. In some embodiments, the method comprises performing a HCl reaction on HCC and gaseous oxygen to produce water. In some embodiments, methods are provided that include contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and bringing the cathode into contact with the catholyte, wherein the cathode is an oxygen depolarization cathode at which the reaction of oxygen and HC1 takes place to produce water. In some embodiments, methods are provided that include contacting the anode with a metal ion in the anolyte in the anode compartment; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the gas diffusion cathode into contact with the catholyte in the cathode compartment; the formation of water at the cathode of HC1 and gaseous oxygen; and bringing an anolyte containing a higher oxidation metal ion into contact with an unsaturated and / or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing an anolyte containing a higher oxidation metal ion into contact with hydrogen gas to obtain an acid , or a combination of both of these processes. In some embodiments, no gas is generated at the gas diffusion cathode. In some embodiments, the method includes an anode on which no gas is generated. In some embodiments, the method includes an anode that does not use gas. In some embodiments, the method further comprises separating the cathode and the anode of the at least one ion exchange membrane. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion located in the anolyte, the anode being configured to convert or oxidize the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a gas diffusion cathode in contact with the catholyte, wherein the cathode is configured to receive water from HC1. In some embodiments, the gas diffusion cathode is an oxygen depolarization (QCD) cathode. In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion located in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a cathode compartment including a gas diffusion cathode in contact with the catholyte, wherein the cathode is configured to receive water from HC1; and a reactor operably connected to the anode compartment and configured to contact an anolyte containing a metal ion of a higher oxidation state and an unsaturated and / or saturated hydrocarbon and / or gaseous hydrogen to produce a halogenated hydrocarbon and acid, respectively. In some embodiments, the device is configured such that no gas is generated at the gas diffusion cathode. In some embodiments, the device is configured such that no gas forms at the anode. In some embodiments, the device is designed such that no gas is used at the anode. In some embodiments, the device further includes at least one ion-exchange membrane separating the cathode and anode. In some embodiments, the ion exchange membrane is a cation exchange membrane (KOM), an anion exchange membrane (AOM), or a combination thereof.

In some embodiments, as illustrated in FIG. 5B, a combination of a gas diffusion cathode (e.g., QCD) and an anode in an electrochemical cell can lead to the formation of water in the cathode compartment. In some embodiments, the electrochemical device 500 includes a gas diffusion cathode in contact with catholyte 501 and an anode in contact with anolyte 502. The following are reactions that can occur at the anode and cathode:

2Н * + 1 / 20g + 2е - Н ₂ 0 (cathode)

Μ ^{ί +} M ^{n +} + xe '(anode, where x = 1-3)

For example, 2Ре ^{g +} -> 2Ре ³⁺ + 2е '(anode)

2Сг ²⁺ -> 2Сг ³⁺ + 2е '(anode)

5p ²⁺ -> 5p ⁴⁺ + 2e (anode)

2Ci * - 2Ci ²⁺ + 2e (anode)

M ^H + formed at the anode combines with chloride ions to form the metal chloride MC1n, for example, but not limited to, PcCb, CrC1 ₃ , §cC1 ₄ or CuC1 ₂ , etc. Oxygen at the cathode can be from

- 30,024,710 atmospheric air or from any commercially available source of oxygen. It should be understood that one AOM depicted in FIG. 5B is for illustrative purposes only, and the device can be designed in such a way that it includes KOM, and HC1 is fed into the anolyte, and hydrogen ions pass through the KOM to catholyte. In some embodiments, the device illustrated in FIG. 5B may contain both AOM and KOM, and the middle compartment may contain chloride salt.

In some embodiments, the electrochemical devices of the present invention can be combined with other electrochemical cells to provide an efficient low energy system. For example, in some embodiments, as illustrated in FIG. 5C, the electrochemical device 400 shown in FIG. 4B can be combined with another electrochemical cell in such a way that the hydrochloric acid formed in the other electrochemical cell is fed into the catholyte of the device 400. The electrochemical device 400 can be replaced by the device 100A (FIG. 1A), 100B (FIG. 1B), 200 (FIG. 2), 400 (FIG. 4A), 500 (FIGS. 5A and 5B), except that the cathode compartment is modified to receive HC1 from another electrochemical cell and oxidize it to produce hydrogen gas. Chloride ions migrate from catholyte to anolyte via AOM. This can lead to a general increase in the voltage in the device, for example, the theoretical cell voltage in the device can be from 0.1 to 0.7 V. In some embodiments, if the cathode is QCD, the theoretical cell voltage can be from -0.5 to -1V. Electrochemical cells producing HC1 in anolyte are described in US patent application No. 12/503557, filed July 15, 2009, which is hereby incorporated by reference in its entirety. Other sources of HC1 are well known in the art. An example of a HC1 source in the form of a process for the production of vinyl chloride monomer (MVC) and its integration into the electrochemical device of this invention is illustrated below in FIG. 8B.

In some embodiments of the methods and devices described herein, a size exclusion membrane (SEM) is used in combination with or in place of an anion exchange membrane (AOM). In some embodiments, the surface of the AOM is coated with a SEM layer. In some embodiments, the SEM is glued or pressed onto the AOM. The use of SEM together with AOM or instead of AOM can prevent the migration of a metal ion or a metal ion connected to the ligand from the anolyte to the catholyte due to the large size of the metal ion per se or connected to the ligand. This can further prevent clogging of KOM or contamination of the catholyte with a metal ion. It should be understood that this use of SEM in combination with AOM or instead of AOM will further facilitate the migration of chloride ions from the third electrolyte to the anolyte. In some embodiments, methods are provided that include contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and preventing the migration of metal ions from the anolyte to the catholyte by using a size exclusion membrane. In some embodiments, the method further includes a cathode that produces alkali in a catholyte, or an oxygen depolarization cathode that produces an alkali in catholyte, or an oxygen depolarization cathode that produces water in a catholyte, or a cathode that produces hydrogen gas. In some embodiments, this method further includes contacting the anolyte containing the metal ion with a higher oxidation state into contact with an unsaturated or saturated hydrocarbon to obtain a halogenated hydrocarbon, or bringing the anolyte containing the metal ion with a higher oxidation state into contact with hydrogen gas to get acid, or a combination of both of these processes. In some embodiments, the unsaturated hydrocarbon in such methods is ethylene. In some embodiments, the metal ion in such methods is copper chloride. In some embodiments, the unsaturated hydrocarbon in such methods is ethylene, and the metal ion is copper chloride. An example of a halogenated hydrocarbon that can be obtained from ethylene is ethylene dichloride, EDC.

In some embodiments, devices are provided that include an anode in contact with the anolyte and configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a size exclusion membrane located between the anode and cathode and configured to prevent the migration of metal ions from the anolyte to the catholyte. In some embodiments, this device further includes a cathode that is configured to produce alkali in a catholyte or to obtain water in a catholyte or to produce hydrogen gas. In some embodiments, this device further includes an oxygen depolarization cathode that is configured to produce alkali and / or water in a catholyte. In some embodiments, this device further includes a cathode on which hydrogen gas is generated. In some embodiments, this device further includes a reactor operably connected to the anode compartment and configured to bring an anolyte containing a metal ion of a higher oxidation state into contact with an unsaturated or saturated hydrocarbon to produce a halogenated hydrocarbon, or to bring an anolyte containing ion metal in a higher oxidation state, in contact with hydrogen gas to obtain acid, or a combination of both of these processes. IN

- 31,047,710 in some embodiments, the unsaturated hydrocarbon in such devices is ethylene. In some embodiments, the metal ion in such devices is copper chloride. In some embodiments, the unsaturated hydrocarbon in such devices is ethylene, and the metal ion is copper chloride. An example of a halogenated hydrocarbon that can be obtained from ethylene is EDC.

In some embodiments, the size-exclusion membrane, as defined above in the text of this description, completely prevents the migration of the metal ion into the cathode compartment or into the middle compartment with the third electrolyte, or reduces migration by 100%, or 99%, or 95%, or 75%, or 50%, or 25%, or 25-50%, or 50-75%, or 50-95%.

In some embodiments, the AOM used in the methods and devices of this invention is resistant to organic compounds (such as ligands or hydrocarbons), so that the AOM does not interact with organic substances and / or the AOM does not react with or absorb metal ions . This can be achieved, only as an example, by using a polymer that does not contain free radicals or anions capable of reacting with organic substances or with metal ions. By way of example only, a polymer containing a fully quaternized (quaternary) amine can be used as AOM. Other examples of AOM are described in this text.

In some embodiments, the metal obtained in the higher oxidation state in the anolyte is subjected to reactions that can lead to the corresponding oxidation products (halogenated hydrocarbon and / or acid), as well as to the metal reduced to the lower oxidation state. A metal ion of a lower oxidation state can then be recycled back to an electrochemical device to form a metal ion of a higher oxidation state. Such reactions conducted to regenerate a metal ion to a lower oxidation state from a metal ion to a higher oxidation state include, but are not limited to, the reactions with gaseous hydrogen or hydrocarbons described herein.

The reaction with hydrogen gas, an unsaturated hydrocarbon and a saturated hydrocarbon.

In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion or oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and treating the metal ion to a higher degree of oxidation with gaseous hydrogen. In some embodiments of the method, the method comprises contacting the cathode with catholyte and the formation of alkali in catholyte. In some embodiments of the method, the method includes contacting the cathode with catholyte and forming alkali and / or hydrogen gas at the cathode. In some embodiments of the method, the method includes contacting the cathode with catholyte and the formation of alkali, water and / or hydrogen gas at the cathode. In some embodiments of the method, the method comprises contacting the gas diffusion cathode with catholyte and producing alkali at the cathode. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion of the metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; the formation of alkali, water or hydrogen gas at the cathode; and treating the metal ion in a higher oxidation state located in the anolyte with hydrogen gas from the cathode. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion of the metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode with oxygen depolarization into contact with the catholyte; the formation of alkali or water at the cathode; and treating the metal ion in a higher oxidation state located in the anolyte with hydrogen gas. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion of the metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; the formation of water or hydrogen gas at the cathode; and treating the metal ion in a higher oxidation state located in the anolyte with hydrogen gas. In some embodiments, the treatment of the metal ion to a higher degree of oxidation with hydrogen gas can be carried out inside the cathode compartment or outside the cathode compartment. In some embodiments, the aforementioned methods include the formation of hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydroiodic acid and / or sulfuric acid by treating a metal ion with a higher degree of oxidation with hydrogen gas. In some embodiments, treating the metal ion with a higher degree of oxidation with hydrogen gas leads to the formation of hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydrogen iodide and / or sulfuric acid and a lower oxidation metal ion . In some embodiments, the lower oxidation metal ion is recycled back to the anode compartment. In some embodiments, the lower oxidation metal acid mixture is subjected to acid removal techniques to separate the lower oxidation metal ion from the acid before the lower oxidation metal ion is recycled back to the anode compartment. .

In some embodiments of the above methods, chlorine gas is not formed at the anode in this method.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with hydrogen gas. In some embodiments of these devices, the device includes a cathode compartment, including a cathode with catholyte, while the cathode is made with the possibility of alkali formation in catholyte. In some embodiments of these devices, the device includes a cathode compartment including a cathode with catholyte, while the cathode is configured to produce hydrogen gas in catholyte. In some embodiments of these devices, the device includes a cathode compartment, including a cathode with catholyte, while the cathode is configured to produce alkali and hydrogen gas in catholyte. In some embodiments of these devices, the device includes a gas diffusion cathode with catholyte, while the cathode is configured to produce alkali in the catholyte. In some embodiments of these devices, the device includes a gas diffusion cathode with catholyte, while the cathode is configured to receive water in the catholyte. In some embodiments, devices are provided that include an anode compartment including an anode with a metal ion in the anolyte, the anode configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; a cathode compartment including a cathode with catholyte, wherein the cathode is configured to produce alkali and / or hydrogen gas in catholyte; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with hydrogen gas from the cathode. In some embodiments, the reactor is operatively connected to the anode compartment and is configured to react an anolyte containing a metal ion of a higher oxidation state with hydrogen gas from the cathode of the same electrochemical cell or with hydrogen gas from an external source. In some embodiments, the treatment of a metal ion to a higher degree of oxidation with hydrogen gas may occur inside the cathode compartment or outside the cathode compartment. In some embodiments, the aforementioned devices include the formation of hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydroiodic acid and / or sulfuric acid by reacting or treating the metal ion to a higher degree of oxidation with hydrogen gas. In some embodiments, treating the metal ion to a higher degree of oxidation with hydrogen gas leads to the formation of hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydrogen iodide and / or sulfuric acid and a metal ion in a lower oxidation state. In some embodiments, the device is configured to receive a metal ion of a lower oxidation state from a metal ion of a higher oxidation state and hydrogen gas, and to recycle the metal ion of a lower oxidation state back to the anode compartment. In some embodiments, the device is configured to separate a metal ion of a lower oxidation state from acid using acid removal techniques, for example, but not limited to, ion exchange resins, size exclusion membranes, acid dialysis, etc.

In some embodiments of the aforementioned devices, the anode in the device is configured such that chlorine gas does not form on it.

In some embodiments, a reaction of a metal obtained to a higher degree of oxidation in the anolyte of the electrochemical devices depicted in FIG. 1A, 1B, 2, 3A, 3B, 4A, 4B, 5A and 5B, with gaseous hydrogen, to obtain the corresponding products, depending on the anion bound to the metal. For example, metal chloride, metal bromide, metal iodide or metal sulfate after the reaction of hydrogen gas with a metal halide or metal sulfate can lead to the formation of the corresponding hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrobromic acid, hydrogen iodide, hydrogen iodide acid or sulfuric acid, respectively. In some embodiments, hydrogen gas is supplied from an external source. In some embodiments, for example, illustrated in FIG. 4A or 4B, hydrogen gas reacting with a metal halide or sulfate is hydrogen gas formed at the cathode. In some embodiments, hydrogen gas is obtained by combining hydrogen from an external source and hydrogen gas obtained at the cathode. In some embodiments, the reaction of the metal halide or sulfate with hydrogen gas leads to the formation of the products described above, as well as the metal halide or sulfate to a lower oxidation state. A metal ion of a lower oxidation state can then be recycled back to an electrochemical device to produce a metal ion of a higher oxidation state.

An example of the electrochemical device depicted in FIG. 5A is illustrated in FIG. 6. It should be understood that the device 600 shown in FIG. 6 is for illustrative purposes only.

- 33,024,710 goals; for this device, other metal ions with different oxidation states (for example, chromium, tin, etc.) and other electrochemical devices are equally applicable, in the cathode compartment of which products other than alkali are formed, for example, water (as in FIG. 5B) or hydrogen gas (as in FIG. 4A or 4B). In some embodiments, as illustrated in FIG. 6, the electrochemical device 600 includes an oxygen depolarization cathode that produces hydroxide ions from water and oxygen. The device 600 also includes an anode that converts metal ions from an oxidation state of 2+ to an oxidation state of 3+ (or from an oxidation state of 2+ to an oxidation state of 4+, for example, for δη, etc.). M ³ + ions combine with chloride ions to form MC1 ₃ . Then, the metal chloride MC1 ₃ reacts with hydrogen gas, as a result of which the metal ion is reduced to a higher oxidation state to form MC12. MS12 is then recycled back to the anode compartment to turn it into MC1 ₃ . In this process, hydrochloric acid is formed, which can be used for commercial purposes or can be used in other processes, as described in this text. In some embodiments, HC1 obtained by this method can be used to dissolve minerals to produce divalent cations that can be used in carbonate precipitation processes, as described herein. In some embodiments, a metal halide or metal sulfate (FIG. 6) can be reacted with an unsaturated or saturated hydrocarbon, as described herein (not shown in the drawings). In some embodiments, the cathode is not a gas diffusion cathode, but is the cathode described in FIG. 4A or 4B. In some embodiments, device 600 can be applied to any electrochemical device that produces alkali.

The text of this description provides some examples of reactors in which a metal compound is reacted with hydrogen gas. As an example in FIG. 7A illustrates a reactor, for example, a reaction column for reacting a metal ion with a higher oxidation state (obtained as shown in the drawings) with hydrogen gas. In some embodiments, as illustrated in FIG. 7A, anolyte is passed through a reaction column. Gas containing hydrogen is also fed to the reaction column. Excess hydrogen gas can be discharged from the reaction column; it can be assembled and moved back to the reaction column. Within the reaction column anolyte containing metal ions in a higher oxidation state (illustrated as the ReS1 _3), may react with hydrogen gas to form HC1 and metal ions in a lower oxidation state, i.e., reduced form, illustrated as FeCl ₂ . The reaction column may contain activated carbon or carbon, or, alternatively, activated carbon may be present outside the reaction column. The reaction of a metal ion with hydrogen gas can occur on activated carbon, from which the reduced anolyte can be regenerated; or activated carbon can simply play the role of a filter to remove impurities from gases. A reduced anolyte containing HC1 and lower oxidation metal ions can be subjected to an acid recovery process using separation methods or acid removal techniques known in the art, including, but not limited to, ion exchange resins, size exclusion membranes and dialysis acids, etc., to separate HC1 from the anolyte. In some embodiments, the ligands described herein can facilitate the separation of the metal ion from the acidic solution due to the large size of the ligand attached to the metal ion. Anolyte containing a metal ion in a lower oxidation state can be recycled back to the electrochemical cell, and HC1 can be collected.

As another example of a reactor, the reaction of a higher oxidation metal ion (obtained as shown in the drawings) with hydrogen gas is also illustrated in FIG. 7B. As illustrated in FIG. 7B, an anolyte from the anode compartment containing metal ions of a higher oxidation state, for example, but not limited to, Fe ³ +, δη ⁴ +, Cr ³ ', etc., can be used to carry out a reaction with hydrogen gas to form HC1 , or can be used to flush a gas containing 8O ₂ to obtain pure gas or sulfuric acid. In some embodiments, it is believed that it is possible to react газовχ gases with metal ions to a higher oxidation state to produce nitric acid. In some embodiments, as illustrated in FIG. 7B, anolyte is passed through a reaction column. A gas containing hydrogen, 8O ₂ and / or NO _X is also fed to the reaction column. Excess hydrogen gas can be discharged from the reaction column; it can be collected and transferred back to the reaction column. Excess 8O ₂ can be passed through a scrubber before releasing cleaner gas to the atmosphere. Inside the reaction column, the anolyte containing metal ions of a higher oxidation state can react with gaseous hydrogen and / or 8О ₂ to form НС1 and / or Н ₂ 8О ₄ and metal ions in a lower oxidation state, i.e. in reduced form. The reaction column may contain activated carbon or carbon, or, alternatively, activated carbon may be present outside the reaction column. The reaction of the metal ion with gaseous hydrogen or gaseous 8O ₂ can occur on activated carbon, from which the reduced anolyte can be regenerated, or activated carbon can simply act as a filter to remove impurities from the gases. Of the reduced anolyte containing HC1 and / or H ₂ 8O ₄ and metal ions in a lower oxidation state,

- 34,024,710 to extract acid using separation methods known in the art, including, but not limited to, the use of ion exchange resins, size exclusion membranes and acid dialysis, etc., to separate HC1 and / or H ₂ §0 ₄ from anolyte. In some embodiments, the ligands described herein can facilitate the separation of the metal ion from the acidic solution due to the large size of the ligand attached to the metal ion. An anolyte containing a metal ion in a lower oxidation state can be recycled back to the electrochemical cell, and HC1 and / or H ₂ §0 ₄ can be collected. In some embodiments, the reaction within the reaction column may take from 1 to 10 hours at a temperature of 50-100 ° C.

An example of the use of an ion exchange resin to separate HC1 from a metal-containing anolyte is shown in FIG. 7C. As illustrated in FIG. 7C, the separation process may include the preferred adsorption / absorption of the inorganic acid on the anion exchange resin. In the first stage, the anolyte containing HC1 and / or H ₂ §0 ₄ is passed through an ion exchange resin that adsorbs HC1 and / or H ₂ §0 ₄ , and thus separates them from the anolyte. HC1 and / or H ₂ §0 ₄ can be regenerated from the resin again by washing the resin with water. Another way to separate the acid from the anolyte can be diffusion dialysis. In some embodiments, the ligands described herein may facilitate the separation of the metal ion from the acidic solution due to the large size of the ligand attached to the metal ion.

In some embodiments, the hydrochloric acid obtained in the process is partially or fully used to dissolve the scrap of ferrous metals to obtain FeCl ₂ and hydrogen gas. The FeCl ₂ obtained in the process can be recycled back to the anode compartment for conversion to FeCl ₃ . In some embodiments, gaseous hydrogen can be used in hydrogen fuel cells. The fuel cell, in turn, can be used to generate electricity to power the electrochemical device described herein. In some embodiments, hydrogen gas is transferred to the electrochemical devices described in US Provisional Application No. 61/477097, which is incorporated herein by reference in its entirety.

In some embodiments, hydrochloric acid with or without a metal ion of a lower oxidation state is subjected to another electrochemical process to produce hydrogen gas and a metal ion of a higher oxidation state. Such a device is illustrated in FIG. eleven.

In some embodiments, the hydrochloric acid obtained in the process is used to produce ethylene dichloride, as illustrated below:

2СиС1 (aq) + 2НС1 (aq) + 1 / 2О _g (gas) -> 2СиС1 _g (water) + Н ₂ О (liquid)

СГН ₄ (gas) + 2СиС1 ₂ (aq) -> 2СиС1 (aq) + С2Н4С12 (liquid)

In some embodiments, it is possible to react the resulting metal to a higher oxidation state in the anolyte of the electrochemical device shown in FIG. 1A, 1B, 2, 3A, 3B, 4A, 4B, 5A, 5B and 5C, with unsaturated hydrocarbons to obtain the corresponding halogenated hydrocarbons or sulfonated hydrocarbons, depending on the anion attached to the metal. For example, metal chloride, metal bromide, metal iodide or metal sulfate, etc. can form the corresponding chlorinated hydrocarbons, brominated hydrocarbons, iodinated hydrocarbons or sulfonated hydrocarbons after the reaction of unsaturated hydrocarbons with a metal halide or metal sulfate. In some embodiments, the reaction of the metal halide or metal sulfate with unsaturated hydrocarbons results in the products described above, as well as the metal halide or sulfate in a lower oxidation state. The lower oxidized metal ion can then be recycled back to the electrochemical device to produce the higher oxidized metal ion.

The term “unsaturated hydrocarbon” as used throughout this specification includes a hydrocarbon with an unsaturated carbon or a hydrocarbon with at least one double and / or at least one triple bond between adjacent carbon atoms. The unsaturated hydrocarbon may be linear, branched or cyclic (aromatic or non-aromatic). For example, the hydrocarbon may be olefinic, acetylene, non-aromatic, for example, cyclohexane, an aromatic group, or substituted with an unsaturated hydrocarbon, for example, but not limited to, a halogenated unsaturated hydrocarbon. Hydrocarbons with at least one double bond can be called olefins or alkenes, and they can have the general formula of an unsubstituted alkene C _p H _2n , where n is 2-20 or 2-10 or 2-8 or 2-5. In some embodiments, one or more hydrogen atoms in the alkene can be further substituted with other functional groups, for example, not limited to halogen (including chlorine, bromine, iodine and fluorine), carboxyl group (-COOH), hydroxyl group (-OH), amino groups etc. Unsaturated hydrocarbons include all isomeric forms of unsaturation, for example, but not limited to, cis and trans isomers, E and Ζ isomers, positional isomers, etc.

In some embodiments, the unsaturated hydrocarbon in the methods and devices provided herein has the formula I, which, after halogenation or sulfonation (including sulfation)

- 35,074,710 gives a compound with the formula II t

(Ute * _C H (; _ _{w n)} -> (Kbsch-SdNsaTsts, ^))

I II where η is 2-10; t is 0-5; C.] is 1-5;

K is independently selected from hydrogen, halogen, —COOC ′, —OH and —ΝΚ ′ (Κ), where K ′ and K are independently selected from hydrogen, alkyl, and substituted alkyl;

X is a halogen selected from fluoro, chloro, bromo and iodo; -8O ₃ N or -O8O ₂ OH.

It should be understood that substituents K can be on one carbon atom or on more than one carbon atom, depending on the number of K and carbon atoms. By way of example only, if η is 3, and m is 2, substituents K can be on the same carbon atom, or on two different carbon atoms.

In some embodiments, the unsaturated hydrocarbon in the methods and devices provided in the text of this description has the formula I, which after halogenation gives a compound with the formula II, in which η is 2-10; t is 0-5; C.] is 1-5; K is independently selected from hydrogen, halogen, -COOK ', -OH and -ΝΡ' (Ρ). where K 'and K are independently selected from hydrogen, alkyl, and substituted alkyl; and X is a halogen selected from chlorine, bromine and iodine.

In some embodiments, the unsaturated hydrocarbon in the methods and devices provided herein has the formula I, which after halogenation leads to a compound with the formula II, in which η is 2-5; t is 0-3; and c.] is 1-4; K is independently selected from hydrogen, halogen, —COOK ′, —OH and —NK ′ (K), where K ′ and K are independently selected from hydrogen and alkyl; and X is a halogen selected from chlorine and bromine.

In some embodiments, the unsaturated hydrocarbon in the methods and devices provided herein has the formula I, which after halogenation leads to a compound with the formula II, in which η is 2-5; t is 0-3; but with | equal to 1-4; K is independently selected from hydrogen, halogen, and —OH, and X is halogen selected from chloro and bromo.

It should be understood that if m is greater than 1, then the substituents K can be on the same carbon atom or on different carbon atoms. Similarly, it should be understood that if c.] Is greater than 1, then X substituents can be on the same carbon atom or on different carbon atoms.

In some embodiments, for the above described embodiments with the formula I, t is 0, and with | equal to 1-2. In such embodiments, X is chlorine.

Examples of substituted or unsubstituted alkenes having the formula I include, but are not limited to, ethylene, chloroethylene, bromethylene, iodoethylene, propylene, chloropropylene, hydroxypropylene, 1 butylene, 2-butylene (cis or trans), isobutylene, 1,3-butadiene pentylene, hexene, cyclopropylene, cyclobutylene, cyclohexene, etc. Hydrocarbons with at least one triple bond can be called alkynes, and they can have the general formula of unsubstituted alkyn C _n H _2n-2 , where η is 2-10 or 2-8 or 2-5. In some embodiments, one or more hydrogen atoms in alkynes can be further substituted with other functional groups, for example, but not limited to, halogen, carboxyl group, hydroxyl group, etc.

In some embodiments, the unsaturated hydrocarbon in the methods and devices provided in the text of this description has the formula ΣΆ, which after halogenation or sulfonation (including sulfation) leads to a compound with the formula PL

Τ '(®) m * C ₀ Hp _n . 1). _t

ΙΑ PA where η is 2-10; t is 0-5; C.] is 1-5;

K is independently selected from hydrogen, halogen, —COOC ′, —OH, and К K ′ (K), where K ′ and K are independently selected from hydrogen, alkyl, and substituted alkyl; and

X is a halogen selected from fluoro, chloro, bromo and iodo; -8O ₃ N or -O8O ₂ OH.

Examples of substituted or unsubstituted alkynes include, but are not limited to, acetylene, propyne, chlorpropine, brompropine, butine, pentine, hexine, etc.

It should be understood that substituents K can be on one carbon atom or on more than

- 36,024,710 to one of the carbon atoms, depending on the number of K and carbon atoms. By way of example only, if η is 3 and m is 2, then K substituents can be on the same carbon atom or on two different carbon atoms.

In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion or oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and treating the anolyte containing the higher oxidation metal ion with an unsaturated hydrocarbon. In some embodiments of the method, the method includes contacting the cathode with catholyte and producing alkali at the cathode. In some embodiments of the method, the method includes contacting the cathode with catholyte and producing alkali, water and / or hydrogen gas at the cathode. In some embodiments of the method, the method comprises contacting the gas diffusion cathode with catholyte and producing alkali or water at the cathode. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion of the metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; obtaining alkali, water and / or hydrogen gas at the cathode; and treating the anolyte, including the higher oxidation metal ion, with an unsaturated hydrocarbon. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; transfer of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the gas diffusion cathode into contact with the catholyte; obtaining alkali or water at the cathode; and treating the anolyte containing the higher oxidation metal ion with an unsaturated hydrocarbon. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion of the metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the gas diffusion cathode into contact with the catholyte; getting alkali at the cathode; and treating the anolyte containing the higher oxidation metal ion with an unsaturated hydrocarbon. In some embodiments, the treatment of a higher oxidation state of the unsaturated hydrocarbon with a metal ion can be carried out inside the cathode compartment or outside the cathode compartment. In some embodiments, treating the metal ion with a higher oxidation state with an unsaturated hydrocarbon results in chlorinated, brominated, iodinated or sulfonated hydrocarbons and the metal ion having a lower oxidation state. In some embodiments, the lower oxidation metal ion is recycled back to the anode compartment.

In some embodiments of the above methods, chlorine gas is not obtained at the anode. In some embodiments of the above methods, treating the unsaturated hydrocarbon with a metal ion in a higher oxidation state does not require gaseous oxygen and / or gaseous chlorine. In some embodiments of the above methods, chlorine gas is not obtained at the anode, and treatment of the unsaturated hydrocarbon with a metal ion in a higher oxidation state does not require oxygen gas and / or chlorine gas.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion located in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with an unsaturated hydrocarbon. In some embodiments of the devices, the device includes a cathode compartment, including a cathode with catholyte, while the cathode is configured to produce alkali, water and / or hydrogen gas in the catholyte. In some embodiments of the devices, the device includes a cathode compartment, including a cathode with catholyte, while the cathode is configured to produce alkali and / or hydrogen gas in the catholyte. In some embodiments of the devices, the device includes a gas diffusion cathode with catholyte, while the cathode is configured to produce alkali or water in the catholyte. In some embodiments, devices are provided that include an anode compartment including an anode with a metal ion located in the anolyte, the anode configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; a cathode compartment, including a cathode with catholyte, while the cathode is configured to form alkali, water or hydrogen gas in the catholyte; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with an unsaturated hydrocarbon. In some embodiments, devices are provided that include an anode compartment including an anode with a metal ion located in the anolyte, the anode configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; a cathode compartment including a gas diffusion cathode with catholyte, wherein the cathode is configured to produce alkali in a catholyte; and a reactor operatively coupled to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with unsaturated carbon-37 024710 hydrogen. In some embodiments, the treatment of a metal ion to a higher degree of oxidation with an unsaturated hydrocarbon can be carried out inside the cathode compartment or outside the cathode compartment. In some embodiments, treating the metal ion with a higher oxidation state with an unsaturated hydrocarbon results in chlorinated, brominated, iodinated or sulfonated hydrocarbons and the metal ion having a lower oxidation state. In some embodiments, the device is configured to produce a metal ion of a lower oxidation state by reacting a metal ion of a higher oxidation state with an unsaturated hydrocarbon and recycling the metal ion of a lower oxidation state back to the anode compartment.

In some embodiments, the unsaturated hydrocarbon in the above embodiments of the method and device, as described herein, has the formula I or is a C ₂ -C ₁₀ alkene or a C ₂ -C ₅ alkene. In some embodiments of the methods and devices described above, the unsaturated hydrocarbon in the above embodiments, as described herein, is ethylene. A halogenated hydrocarbon obtained from such an unsaturated hydrocarbon has the formula II (as described herein), for example, ethylene dichloride, chloroethanol, butyl chloride, dichlorobutane, chlorobutanol, etc. In some embodiments of the methods and devices described above, the metal ion is a metal ion described herein, for example, but not limited to, copper, iron, tin, or chromium.

In some embodiments of the devices described above, the anode is configured such that chlorine gas does not form on it. In some embodiments of the devices described above, a reactor configured to react a unsaturated hydrocarbon with a metal ion to a higher oxidation state is designed so that it does not require gaseous oxygen and / or gaseous chlorine. In some embodiments of the above methods, the anode is configured such that chlorine gas is not formed on it, and the reactor is configured such that it does not require oxygen gas and / or chlorine gas.

An example of the electrochemical device depicted in FIG. 5A is illustrated in FIG. 8A. It should be understood that the device 800 shown in FIG. 8A is provided for illustration only, and other metal ions with different oxidation states, other unsaturated hydrocarbons, and other electrochemical devices that form products other than alkali in the cathode compartment, such as water or hydrogen gas, are equally applicable to this device. In the device shown in FIG. 8A, the cathode shown in FIG. 4A or 4B. In some embodiments, as illustrated in FIG. 8A, the electrochemical device 800 includes an oxygen depolarization cathode that produces hydroxide ions from water and oxygen. The device 800 also includes an anode that converts metal ions from an oxidation state of 1+ to an oxidation state of 2+. Cu ² + ions together with chloride ions to form SiS1 _2. The metal chloride CuCl ₂ can then react with an unsaturated hydrocarbon, for example, but not limited to ethylene, which leads to the reduction of the metal ion to a lower oxidation state to form CuCl and a dichlorinated hydrocarbon, for example, but not limited to ethylene dichloride. CuCl is then recycled back to the anode compartment for conversion to CuCl ₂ .

Ethylene dichloride obtained using the methods and devices of this invention can be used for commercial purposes. In some embodiments, ethylene dichloride is converted to vinyl chloride monomer (MVX) using processes such as cracking / purification. Vinyl chloride monomer can be used in the production of polyvinyl chloride. In some embodiments, hydrochloric acid formed during the conversion of EDC to MVX can be separated and reacted with acetylene to further obtain MVX.

In some embodiments, HC1 obtained during the formation of MBX can be sent to one or more of the electrochemical devices described herein in which HC1 is used in catholyte or anolyte to produce hydrogen gas or water at the cathode. In FIG. 8A illustrates the combined electrochemical device of this invention in combination with the synthesis of MVX / PVC. Any of the electrochemical devices of this invention, for example, the device illustrated in FIG. 1B, 2, 4A or 5A, can be used to obtain CuCl ₂ , which, when reacted with ethylene, gives EDC. The cracking of the EDC followed by processing of the MVX gives HC1, which can be sent to any of the electrochemical devices depicted in FIG. 4V or 5V, for additional obtaining CuCl ₂ . It should be understood that the process as a whole can only be carried out using the device shown in FIG. 4B or 5B (i.e., without turning on the devices depicted in FIG. 1B, 2, 4A, or 5A).

In some embodiments, chlorination of ethylene in an aqueous medium with a higher oxidation rate of metal chloride results in the production of ethylene dichloride, chloroethanol, or a combination thereof. In some embodiments of the methods and devices described herein, more than 10 wt.%, Or more than 20 wt.%, Or more than 30 wt.%, Or more than 40 wt.%, Or more than 50 wt.%, Or more than 60 wt. %, or more than 70 wt.%, or more than 80 wt.%, or more than 90 wt.%, or more than 95 wt.%, or about 99 wt.%, or about 10-99 wt.%, or about 10- 95 wt.%, Or approximately 15-95 wt.%, Or approximately 25-95 wt.%, Or approximately 50-95 wt.%, Or approximately 50-99

38,024,710 wt.% Ethylene dichloride, or about 50-99.9 wt.% Ethylene dichloride, or about 5099,99 wt.% Ethylene dichloride. In some embodiments, the remaining weight percent is chloroethanol. In some embodiments, chloroethanol is not formed in the reaction. In some embodiments, less than 0.001 wt.% Chloroethanol, or less than 0.01 wt.%, Or less than 0.1 wt.%, Or less than 0.5 wt.%, Or less than 1 wt.%, Or less than 5, is formed in the reaction. wt.%, or less than 10 wt.%, or less than 20 wt.%; while the remainder is EDH. In some embodiments, less than 0.001 wt.%, Or less than 0.01 wt.%, Or less than 0.1 wt.%, Or less than 0.5 wt.%, Or less than 1 wt.%, Or less, is present in the EDC product. 5 wt.% Metal ion. In some embodiments, less than 0.001 wt.%, Or less than 0.01 wt.%, Or less than 0.1 wt.% Of chloroethanol and / or metal ion is present in the EDC product.

In some embodiments, the metal EDC EDC product may undergo a washing step, which may include washing with an organic solvent or passing the EDC product through a metal ion removal column. In some embodiments, the EDC product can be purified by distillation, during which any by-products such as chloral (CC1 ₃ CHO) and / or chloral hydrate (2,2,2-trichloroethane-1,1-diol) can be separated if they are are formed.

In some embodiments, the unsaturated hydrocarbon is propene. In some embodiments, a highly oxidized metal ion, for example CuCl ₂ , is treated with propene to give propane dichloride (C ₃ H ₆ Cl ₂ ) or dichloropropane (DCP), which can be used to produce allyl chloride (C ₃ H ₅ C1). In some embodiments, the unsaturated hydrocarbon is butene or butylene. In some embodiments, the metal ion in a higher oxidation state, e.g. SiS1 _2, treated with butene to obtain dichlorobutane (C ₄ H ₈ C1 ₂₎ or dichlorobutene (S4N6S12) which can be used for preparing chloroprene (S4N5S1). In some embodiments, the unsaturated hydrocarbon is benzene. In some embodiments, the highly oxidized metal ion, for example CuCl ₂ , is treated with benzene to produce chlorobenzene. In some embodiments, a highly oxidized metal ion, such as CuCl ₂ , is treated with acetylene to produce chloroacetylene, dichloroacetylene, vinyl chloride, dichloroethene, tetrachloretene, or a combination thereof. In some embodiments, the unsaturated hydrocarbon is treated with a higher oxidation state to produce a product including, but not limited to, ethylene dichloride, chloroethanol, chlorpropene, propylene oxide (subsequently dehydrochlorinated), allyl chloride, methyl chloride, trichlorethylene, tetrachloroethene, chlorobenzene, 1, 2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1,1-dichloroethane, chlorophenol, chlorinated toluene, etc.

In some embodiments, the yield of a halogenated hydrocarbon derived from an unsaturated hydrocarbon, for example, the yield of EDC from ethylene, or the yield of DCP from propylene or dichlorobutene from butene using metal ions is more than 90 wt.%, Or more than 95 wt.%, Or 90 to 95 wt.%, Or from 90 to 99 wt.%, Or from 90 to 99.9 wt.% In some embodiments, the selectivity of a halogenated hydrocarbon derived from an unsaturated hydrocarbon, for example, the exit of EDC from ethylene, or the exit of DC from propylene or dichlorobutene from butene using an ion s metal, is more than 80 wt.%, or more than 90 wt.%, or from 80 to 99 wt.% In some embodiments, the product yield in one pass per unit time per unit volume of contact space (volumetric capacity) for a halogenated hydrocarbon obtained from an unsaturated hydrocarbon, for example, for EDC from ethylene, or for DCP from propylene, or for dichlorobutene from butene, using metal ions, is more than 3, or more than 4, or more than 5, or from 3 to 5, or from 3 to 6, or from 3 to 8.

In some embodiments, a higher oxidation state of the metal formed in the anolyte of the electrochemical devices depicted in FIG. 1A, 1B, 2, 3A, 3B, 4A, 4B, 5A and 5B, with saturated hydrocarbons, to obtain the corresponding halogenated hydrocarbons or sulfonated hydrocarbons, depending on the anion bound to the metal. For example, metal chloride, metal bromide, metal iodide or metal sulfate, etc. may result in the corresponding chlorinated hydrocarbons, brominated hydrocarbons, iodinated hydrocarbons or sulfonated hydrocarbons after the reaction of saturated hydrocarbons with a metal halide or metal sulfate. In some embodiments, the reaction of the metal halide or metal sulfate with saturated hydrocarbons results in the products described above, as well as the metal halide or metal sulfate in a lower oxidation state. Then, a metal ion of a lower oxidation state can be recycled back to the electrochemical device to produce a metal ion of a higher oxidation state.

The term saturated hydrocarbon, as used throughout this specification, includes a hydrocarbon that does not contain unsaturated carbon atoms or hydrocarbons. The hydrocarbon may be linear, branched or cyclic. For example, the hydrocarbon may be substituted or unsubstituted alkanes and / or substituted or unsubstituted cycloalkanes. Hydrocarbons may have the general formula of the unsubstituted alkane SpH2n'2, where n is 2-20, or 2-10, or 2-8, or 2-5. In some embodiments, one or more hydrogen atoms in an alkane or in cycloalkanes can be further replaced by other functional groups, for example, but not limited to, halogen

- 39,024,710 (including chlorine, bromine, iodine and fluorine), a carboxyl group (—COOH), a hydroxyl group (—OH), amines, etc.

In some embodiments, the saturated hydrocarbon in the methods and devices provided in the text of this description has the formula III, which, after halogenation or sulfonation (including sulfation), leads to the compound of formula IV (E) c-Cn (! | 1 + 1Kb * (Yk'SvNsi + gMK + O where n is 2-10; k is 0-5;

equal to 1-5;

K is independently selected from hydrogen, halogen, —COOC ′, —OH, and —XK ′ (K), where K ′ and K are independently selected from hydrogen, alkyl, or substituted alkyl;

X is a halogen selected from fluoro, chloro, bromo and iodo; § О ₃ H or О § § ₂ OH.

It should be understood that the substituents K can be on one carbon atom or more than one carbon atom, depending on the number of K and carbon atoms. By way of example only, if n is 3 and k is 2, then substituents K can be on the same carbon atom or on two different carbon atoms.

In some embodiments, the saturated hydrocarbon in the methods and devices provided in the text of this description has the formula III, which after halogenation leads to a compound with the formula IV, where n is 2-10; k is 0-5; 8 is 1-5; K is independently selected from hydrogen, halogen, —COOC ′, —OH and —YK ′ (K), where K ′ and K are independently selected from hydrogen, alkyl, and substituted alkyl; and X is a halogen selected from chlorine, bromine and iodine.

In some embodiments, the saturated hydrocarbon in the methods and devices provided in the text of this description has the formula III, which after halogenation leads to a compound with the formula IV, where n is 2-5; k is 0-3; a is 1-4; K is independently selected from hydrogen, halogen, —COOK ′, —OH, and —XK ′ (K), where K ′ and K are independently selected from hydrogen and alkyl; and X is a halogen selected from chloro and bromo.

In some embodiments, the saturated hydrocarbon in the methods and devices provided in the text of this description has the formula III, which after halogenation leads to a compound with the formula IV, where n is 2-5; k is 0-3; and 8 is 1-4; K is independently selected from hydrogen, halogen, and —OH, and X is halogen selected from chloro and bromo.

It should be understood that if k is greater than 1, then the substituents K can be on the same carbon atom or on different carbon atoms. Similarly, it should be understood that if 8 is greater than 1, then X substituents may be on the same carbon atom or on different carbon atoms.

In some embodiments of the above examples of embodiments of formula III, k is 0, 8 is 1-2. In such embodiments, X is chlorine.

Examples of substituted or unsubstituted alkanes, for example with formula III, include, but are not limited to, methane, ethane, chloroethane, bromoethane, iodoethane, propane, chloropropane, hydroxypropane, butane, chlorobutane, hydroxybutane, pentane, hexane, cyclohexane, cyclopentane, chlorocyclopent and .d.

In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; the conversion or oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; and treating the anolyte containing the higher oxidation metal ion with a saturated hydrocarbon. In some embodiments of the method, the method comprises contacting the cathode with catholyte and the formation of alkali at the cathode. In some embodiments of the method, the method includes contacting the cathode with catholyte and producing alkali and hydrogen gas at the cathode. In some embodiments of the method, the method includes contacting the cathode with catholyte and producing hydrogen gas at the cathode. In some embodiments of the method, the method comprises contacting the gas diffusion cathode with catholyte and producing alkali at the cathode. In some embodiments of the method, the method includes contacting the gas diffusion cathode with catholyte and producing water at the cathode. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; transfer of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; the formation of alkali, water and / or hydrogen gas at the cathode; and treating the anolyte containing the higher oxidation metal ion with a saturated hydrocarbon. In some embodiments, methods are provided that include bringing the anode into contact with a metal ion located in the anolyte in the anode compartment; transfer of a metal ion at the anode from a lower degree

- 40,047,710 oxidation to a higher oxidation state; bringing the gas diffusion cathode into contact with the catholyte; the formation of alkali or water at the cathode; and treating the anolyte containing the higher oxidation metal ion with a saturated hydrocarbon. In some embodiments, the treatment of a metal ion to a higher degree of oxidation with a saturated hydrocarbon can be carried out inside the cathode compartment or outside the cathode compartment. In some embodiments, treating the metal ion to a higher degree of oxidation with a saturated hydrocarbon results in a halogenated hydrocarbon or sulfonated hydrocarbon, for example, a chlorinated, brominated, iodinated or sulfonated hydrocarbon and a metal ion in a lower oxidation state. In some embodiments, the lower oxidation metal ion is recycled back to the anode compartment. In some embodiments, the saturated hydrocarbon in the above embodiments, as described herein, has the formula III (as described herein) or is a C ₂ C ₁₀ alkane or a C ₂ -C ₅ alkane. In some embodiments, the saturated hydrocarbon in the above embodiments, as described herein, is methane. In some embodiments, the saturated hydrocarbon in the above embodiments, as described herein, is ethane. In some embodiments, the saturated hydrocarbon in the above embodiments, and as described herein, is propane. A halogenated hydrocarbon obtained from such a saturated hydrocarbon has the formula IV (as described herein) and is, for example, chloromethane, dichloromethane, chloroethane, dichloroethane, chlorpropane, dichloropropane, etc.

In some embodiments of the methods described above, the metal ion used is platinum, palladium, copper, iron, tin, and chromium. In some embodiments of the methods described above, chlorine gas is not formed at the anode. In some embodiments of the methods described above, treating a saturated hydrocarbon with a metal ion in a higher oxidation state does not require gaseous oxygen and / or gaseous chlorine. In some embodiments of the methods described above, chlorine gas is not formed at the anode, and treatment of a saturated hydrocarbon with a metal ion in a higher oxidation state does not require oxygen gas and / or chlorine gas.

In some embodiments, devices are provided that include an anode compartment including an anode in contact with a metal ion located in the anolyte, the anode configured to transfer the metal ion from a lower oxidation state to a higher oxidation state; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with a saturated hydrocarbon. In some embodiments of these devices, the device includes a cathode compartment, including a cathode with catholyte, while the cathode is configured to produce alkali on the cathode. In some embodiments of these devices, the device includes a cathode compartment, including a cathode with catholyte, while the cathode is configured to produce hydrogen gas at the cathode. In some embodiments of these devices, the device includes a cathode compartment, including a cathode with catholyte, while the cathode is configured to produce alkali and hydrogen gas at the cathode. In some embodiments of these devices, the device includes a gas diffusion cathode with catholyte, while the device is configured to produce alkali on the cathode. In some embodiments of these devices, the device includes a gas diffusion cathode with a catholyte, while the cathode is configured to receive water at the cathode. In some embodiments, systems are provided that include an anode compartment including an anode with a metal ion located in the anolyte, the anode configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; the cathode compartment comprising a cathode with catholyte, while the cathode is configured to form alkali, water and hydrogen gas in the catholyte; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with a saturated hydrocarbon. In some embodiments, devices are provided that include an anode compartment including an anode with a metal ion located in the anolyte, the anode configured to transfer a metal ion from a lower oxidation state to a higher oxidation state in the anode compartment; a cathode compartment including a gas diffusion cathode with catholyte, wherein the cathode is configured to form alkali or water in the catholyte; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with a saturated hydrocarbon. In some embodiments, the treatment of a metal ion to a higher degree of oxidation with a saturated hydrocarbon can be carried out inside the cathode compartment or outside the cathode compartment. In some embodiments, treating the metal ion with a higher oxidation state with a saturated hydrocarbon results in the formation of chlorinated, brominated, iodinated or sulfonated hydrocarbons and the metal ion with a lower oxidation state. In some embodiments, the device is configured to form a metal ion of a lower oxidation state from a metal ion of a higher oxidation state by reaction with a saturated hydrocarbon, and supply the metal ion of a lower oxidation state back to the anode compartment.

In some embodiments of the methods and devices described above, the metal ion is the 41,047,710 metal ion described herein, for example, but not limited to platinum, palladium, copper, iron, tin, or chromium.

In some embodiments of the devices described above, the anode is configured such that chlorine gas does not form on it. In some embodiments of the devices described above, a reactor configured to react a saturated hydrocarbon with a metal ion to a higher oxidation state is such that it does not require gaseous oxygen and / or gaseous chlorine. In some embodiments of the methods described above, the anode is configured such that chlorine gas is not generated on it and the reactor is configured such that it does not require oxygen gas and / or chlorine gas.

It should be understood that an example of the electrochemical device illustrated in FIG. 8A may be configured to use saturated hydrocarbons by replacing an unsaturated hydrocarbon with a saturated hydrocarbon. Accordingly, suitable metal ions such as platinum chloride, palladium chloride, copper chloride, etc. can be used.

In some embodiments, chlorination of ethane in an aqueous medium with a higher oxidation rate of metal chloride results in the formation of chloroethane, dichloroethane, or a combination thereof. In some embodiments of the methods and devices described herein, more than 10 wt.%, Or more than 20 wt.%, Or more than 30 wt.%, Or more than 40 wt.%, Or more than 50 wt.%, Or more than 60 wt.%, or more than 70 wt.%, or more than 80 wt.%, or more than 90 wt.%, or more than 95 wt.%, or about 99 wt.%, or about 10-99 wt.%, or about 10-95 wt.%, or about 15-95 wt.%, or about 25-95 wt.%, or about 50-95 wt.%, or about 50-99 wt.%, or about 50-99 9 wt.%, Or approximately 50-99.99 wt.% Chloroethane. In some embodiments, the remaining weight percent is chloroethanol and / or ethylene dichloride. In some embodiments, chloroethanol is not formed in the reaction. In some embodiments, less than 0.001 wt.%, Or less than 0.01 wt.%, Or less than 0.1 wt.%, Or less than 0.5 wt.%, Or less than 1 wt.%, Is formed in the reaction in the remaining product. or less than 5 wt.%, or less than 10 wt.%, or less than 20 wt.% chloroethanol. In some embodiments, less than 0.001 wt.%, Or less than 0.01 wt.%, Or less than 0.1 wt.%, Or less than 0.5 wt.%, Or less than 1 wt.%, Or less than 5 wt. .% metal ion. In some embodiments, less than 0.001 wt.%, Or less than 0.01 wt.%, Or less than 0.1 wt.% Of chloroethanol and / or metal ion is present in the product.

In some embodiments, the yield of a halogenated hydrocarbon from a saturated hydrocarbon, for example, the yield of chloroethane or EDC from ethane, when using metal ions, is more than 90 wt.%, Or more than 95 wt.%, Or from 90 to 95 wt.%, Or from 90 up to 99 wt.%, or from 90 to 99.9 wt.%. In some embodiments, the selectivity for a halogenated hydrocarbon derived from a saturated hydrocarbon, for example, the yield of chloroethane or EDC from ethane, when using metal ions, is more than 80 wt. %, or more than 90 wt.%, or from 80 to 99 wt.% In some cases sensations, the product yield in one pass per unit time per unit volume of contact space (volumetric capacity) for a halogenated hydrocarbon from a saturated hydrocarbon is more than 3, or more than 4, or more than 5, or from 3 to 5, or from 3 to 6, or 3 to 8.

Products, for example, but not limited to, halogenated hydrocarbon, acid, carbonate and / or bicarbonate obtained using the methods and devices of this invention are greener than the same products obtained using traditional methods and devices known in the art . Methods for producing a green halogenated hydrocarbon are provided, which include contacting the anode with anolyte; oxidation of metal chloride at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and halogenating the unsaturated or saturated hydrocarbon with a higher oxidation metal chloride to produce a green halogenated hydrocarbon. In some embodiments, a green halogenated hydrocarbon obtained by the methods described herein is provided. A device is also provided that includes an anode in contact with an anolyte, wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably connected to the anode compartment and configured to react the metal ion to a higher oxidation state with an unsaturated or saturated hydrocarbon to produce a green halogenated hydrocarbon.

The terms greener or greener or its grammatical equivalents used in the text of this description include any chemical substance or product obtained using the methods or devices of this invention, which provide higher energy savings or greater voltage reduction compared with the same chemical substance or a product obtained by methods known in the art. For example, a chlor-alkali process is a process that is usually used to produce chlorine gas, and chlorine gas is then used to chlorine ethylene to produce EDC. The amount of energy required to obtain EDC by the chlor-alkali method is higher than the amount of energy required to obtain EDC by the metal oxidation method of this invention. Thus, the EDC obtained using

- 42,024,710 methods and devices according to this invention is more green than the EDC obtained using the chlor-alkali method. Such energy savings are illustrated in FIG. 8C, which illustrates activation barriers for implementing the methods of this invention in comparison with activation barriers for the chlor-alkali method.

As illustrated in FIG. 8C, a comparison is made of the energy required to obtain EDC using a chlor-alkali method and the energy required to obtain EDC using the methods and devices of this invention. The method for producing EDC is illustrated in two parts. The electrochemical part, where the oxidation of copper occurs in device 1 and Device 2 according to this invention, in comparison with the production of chlorine in the chlor-alkali method. The catalytic part, where copper chloride (P) (obtained by the electrochemical method) chlorinates ethylene in devices 1 and 2, and gaseous chlorine (obtained by the chlor-alkali method) chlorinates ethylene (known method) to obtain EDC. In device 1, an electrochemical reaction is carried out in the absence of a ligand, and in device 2, an electrochemical reaction is carried out in the presence of a ligand. In device 1,

The device 2 and in the chlor-alkali method, the cathode is a cathode on which hydrogen gas is formed, and the current density for the electrochemical reaction is 300 mA / cm ² . As illustrated in FIG. 8C for an electrochemical reaction, Device 1 provides energy savings of more than 125 kJ / mol compared to the chlor-alkali method, and Device 2 provides energy savings of more than 225 kJ / mol compared to the chlor-alkali method. Thus, energy savings of up to 300 kJ / mol can be obtained; or up to 250 kJ / mol; or from 50 to 300 kJ / mol; or from 50 to 250 kJ / mol; or from 100 to 250 kJ / mol; or from 100 to 200 kJ / mol upon receipt of a green halogenated hydrocarbon, for example, but not limited to, EDC, using the methods and devices of this invention, compared with the traditional method for producing EDC, for example, chlor-alkali method. This leads to savings of more than 1 MWh per ton of EDC, or from 1 to 21 MWh per ton of EDC for devices 1 and 2 compared to the chlor-alkali method. This also corresponds to a voltage reduction of more than 1 V or from 1 to 2 V (1 V x 2 electron is approximately 200 kJ / mol) compared with the chlor-alkali method.

As also illustrated in FIG. 8C, the catalytic part of the reaction has a low theoretical barrier for each device 1 and 2 and a high barrier for two devices 1 and 2. The catalytic reaction in device 1 and device 2 can occur at a low barrier point or at a high barrier point or at any point between them , depending on the conditions, for example, not limited to this, concentration, reactor size, costs, etc. Even if there is some energy input for the catalytic reactions in device 1 and 2, it will be compensated due to the significant energy savings in the electrochemical reaction, so that the total energy savings is up to 100 kJ / mol, or more than 100 kJ / mol, or from 50 to 100 kJ / mol, or from 0 to 100 kJ / mol. This corresponds to 1 MWh per ton of EDH or more, or a voltage reduction of 0-1 V or more than 1 V or 1-2 V, compared with the chlor-alkali method. It should be understood that both the chlor-alkali method and device 1 and device 2 operate in an aqueous medium. An electrochemical cell or a catalytic system operating in an organic solvent (for example, by partially or completely removing water from an electrochemical cell by azeotropic distillation) may require even more energy than the traditional method, and thus will not produce a green halogenated hydrocarbon.

Also FIG. 8C further illustrates the energy savings in device 2 that a ligand provides, as compared to device 1 where no ligand is used.

Accordingly, methods for producing a green halogenated hydrocarbon are provided, which comprise contacting the anode with anolyte; oxidation of metal chloride at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and halogenating an unsaturated or saturated hydrocarbon with a higher oxidation metal chloride to produce a green halogenated hydrocarbon; however, this method leads to a total energy savings of more than 100 kJ / mol; or more than 150 kJ / mol; or more than 200 kJ / mol; or from 100 to 250 kJ / mol; or from 50 to 100 kJ / mol; or from 0 to 100 kJ / mol; or this method leads to a voltage reduction of more than 1 V or 0-1 V or 1-2 V or 0-2 V. A device is also provided that includes an anode in contact with the anolyte, while the anode is made to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably connected to the anode compartment and configured to react the metal ion to a higher oxidation state with an unsaturated or saturated hydrocarbon to produce a green halogenated hydrocarbon; the device leads to a total energy savings of more than 100 kJ / mol, or more than 150 kJ / mol, or more than 200 kJ / mol, or from 100 to 250 kJ / mol, or from 50 to 100 kJ / mol, or from 0 to 100 kJ / mol; or the device reduces the voltage by more than 1 V or 0-1 V or 1-2 V or 0-2 V.

All electrochemical devices and methods described herein operate in an environment containing 43,024,710 containing more than 5 wt.%, Water or more than 6 wt.%, Water, or in an aqueous medium. In one aspect, these methods and devices provide an advantage in carrying out a metal oxidation reaction in an electrochemical cell and conducting a reduction reaction outside the cell, both in an aqueous medium. Applicants have unexpectedly discovered that the use of an aqueous medium in the halogenation or sulfonation of an unsaturated or saturated hydrocarbon or hydrogen gas not only leads to a high yield of the product and high selectivity for the product (as shown in the examples given here), but also leads to the production of a reduced ion in the aqueous medium metal in a lower oxidation state, which can be recycled back to the electrochemical device. In some embodiments, since the electrochemical cell operates efficiently in an aqueous medium, it is not necessary to remove water from an anolyte containing a higher oxidation metal ion that reacts with an unsaturated or saturated hydrocarbon or hydrogen gas in an aqueous medium (for example, by azeotropic distillation ), or minimal water removal is required. Thus, the use of an aqueous medium both in an electrochemical cell and in a catalytic system provides efficient and less energy-intensive devices and methods according to this invention.

Accordingly, in some embodiments, a method is provided comprising contacting the anode with anolyte, the anolyte containing a metal ion; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and carrying out the reaction of an unsaturated or saturated hydrocarbon with an anolyte containing a metal ion of a higher oxidation state in an aqueous medium; wherein the aqueous medium contains more than 5 wt.%, water, or more than 5.5 wt.%, or more than 6 wt.%, or from 5 to 90 wt.%, or from 5 to 95 wt.%, or from to 99 wt.%, Water, or from 5.5 to 90 wt.%, Or from 5.5 to 95 wt.%, Or from 5.5 to 99 wt.%, Water, or from up to 90 wt.%, or from 6 to 95 wt.%, or from 6 to 99 wt.% water. In some embodiments, a method is provided comprising contacting the anode with anolyte, the anolyte containing a metal ion; oxidizing the metal halide or metal sulfate at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and halogenating or sulfonating an unsaturated or saturated hydrocarbon with a metal halide or metal sulfate at a higher oxidation state in an aqueous medium; wherein the aqueous medium contains more than 5 wt.%, or more than 5.5 wt.%, or more than 6 wt.%, or from 5 to 90 wt.%, or from 5 to 95 wt.%, or from 5 to 99 wt.%, water, or from 5.5 to 90 wt.%, or from 5.5 to 95 wt.%, or from 5.5 to 99 wt.%, water, or from 6 to 90 wt.%, or from 6 to 95 wt.%, or from 6 to 99 wt.% water. Unsaturated hydrocarbons (e.g., with formula I), saturated hydrocarbons (e.g., with formula III), halogenated hydrocarbons (e.g., with formulas II and IV), metal ions, etc. described in detail in this text.

In some embodiments, a method is provided comprising contacting the anode with anolyte; oxidizing the metal halide or metal sulfate at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; and bringing the metal halide or metal sulfate to a higher oxidation state into contact with hydrogen gas in an aqueous medium to produce an acid, for example, hydrochloric acid or sulfuric acid; wherein the aqueous medium contains more than 5 wt.%, water, or more than 5.5 wt.%, or more than 6 wt.%, or from 5 to 90 wt.%, or from 5 to 95 wt.%, or from 5 up to 99 wt.%, water, or from 5.5 to 90 wt.%, or from 5.5 to 95 wt.%, or from 5.5 to 99 wt.%, water, or from 6 to 90 wt. %, or from 6 to 95 wt.%, or from 6 to 99 wt.% water. In some embodiments, the cathode produces hydroxide ions.

In some embodiments of the above methods, water, alkali and / or hydrogen gas are produced at the cathode. In some embodiments of the methods described above, the cathode is a water-generating CCD. In some embodiments of the methods described above, the cathode is an alkali-producing CCD. In some embodiments of the methods described above, the cathode produces hydrogen gas. In some embodiments of the methods described above, the cathode is an oxygen depolarization cathode that reduces oxygen and water to hydroxide ions; the cathode is a hydrogen gas producing cathode, which reduces water to hydrogen gas and hydroxide ions; the cathode is a hydrogen gas producing cathode that reduces hydrochloric acid to hydrogen gas; or the cathode is an oxygen depolarization cathode on which hydrochloric acid and oxygen gas react with the formation of water.

In some embodiments of the above methods, the metal ion is any metal ion described in this text. In some embodiments of the above methods, the metal ion is selected from the group consisting of iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth, titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and their combinations. In some embodiments, the metal ion is selected from the group consisting of iron, chromium, copper and tin. In some embodiments, the metal ion is copper. In some embodiments, the lower oxidation state of the metal ion is 1+, 2+, 3+, 4+, or 5+. In some embodiments, the higher oxidation state of the metal ion is 2+, 3+, 4+, 5+, or 6+.

- 44,047,710

In some embodiments, the method further comprises recycling at least a portion of the lower oxidation metal ion back to the electrochemical cell. In some embodiments, the azeotropic distillation of water is not carried out in this method before the reaction of the metal ion to a higher degree of oxidation with an unsaturated or saturated hydrocarbon.

In some embodiments, in the methods described above, chlorine gas is not formed at the anode. In some embodiments, the methods described above do not require gaseous oxygen and / or gaseous chlorine to chlorinate an unsaturated or saturated hydrocarbon to a chlorinated hydrocarbon.

In some embodiments, a device is provided comprising an anode in contact with an anolyte containing a metal ion, wherein the anode is configured to oxidize a metal ion from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably connected to the anode compartment and configured to react an anolyte containing a metal ion of a higher oxidation state with an unsaturated hydrocarbon or saturated hydrocarbon in an aqueous medium; wherein the aqueous medium contains more than 5 wt.%, water, or more than 5.5 wt.%, or more than 6 wt.%, or from 5 to 90 wt.%, or from 5 to 95 wt.%, or from 5 up to 99 wt.%, water, or from 5.5 to 90 wt.%, or from 5.5 to 95 wt.%, or from 5.5 to 99 wt.%, water, or from 6 to 90 wt. %, or from 6 to 95 wt.%, or from 6 to 99 wt.% water. In some embodiments, there is provided a device comprising an anode in contact with an anolyte and configured to oxidize at the anode a metal halide or metal sulfate from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably connected to the anode compartment and configured to halogen or sulfonate the unsaturated or saturated hydrocarbon with a metal halide or sulfate to a higher degree of oxidation in an aqueous medium; wherein the aqueous medium contains more than 5 wt.%, water, or more than 5.5 wt.%, or more than 6 wt.%, or from 5 to 90 wt.%, or from 5 to 95 wt.%, or from 5 up to 99 wt.%, water, or from 5.5 to 90 wt.%, or from 5.5 to 95 wt.%, or from 5.5 to 99 wt.%, water, or from 6 to 90 wt. %, or from 6 to 95 wt.%, or from 6 to 99 wt.% water.

In some embodiments, there is provided a device comprising an anode in contact with an anolyte configured to oxidize a metal halide or metal sulfate at the anode from a lower oxidation state to a higher oxidation state; cathode in contact with catholyte; and a reactor operably connected to the anode compartment and configured to contact the metal halide or sulfate of a higher oxidation state with hydrogen gas in an aqueous medium to form an acid, for example, hydrochloric acid or sulfuric acid; wherein the aqueous medium contains more than 5 wt.%, water, or more than 5.5 wt.%, or more than 6 wt.%, or from 5 to 90 wt.%, or from 5 to 95 wt.%, or from 5 up to 99 wt.%, water, or from 5.5 to 90 wt.%, or from 5.5 to 95 wt.%, or from 5.5 to 99 wt.%, water, or from 6 to 90 wt. %, or from 6 to 95 wt.%, or from 6 to 99 wt.% water.

In some embodiments of the devices described above, the cathode is configured to produce a hydroxide ion. In some embodiments of the devices described above, the cathode is configured to produce hydrogen gas. In some embodiments of the devices described above, the cathode is configured to receive water. In some embodiments of the devices described above, the cathode is a QCD. In some embodiments of such methods and devices, azeotropic distillation of water is not required to reduce the amount of water in the anolyte. In some embodiments, the device further includes a separator operably coupled to a reactor that separates the product, for example acid or halogenated hydrocarbon, from the metal ion to a lower oxidation state. In some embodiments, the device further includes a recirculation system operably connected to the separator and the anode compartment of the electrochemical device, configured to recycle at least a portion of the metal ion of a lower oxidation state from the separator back to the electrochemical cell. Such a recirculation system may be a pipe, pipe, tube, etc., which can be used to move the solutions. Associated control valves and computer control systems may be associated with such recirculation systems.

In some embodiments, the devices described above are configured such that chlorine gas does not form on the anode. In some embodiments, the devices described above are such that they do not require gaseous oxygen and / or gaseous chlorine to chlorinate an unsaturated or saturated hydrocarbon to a halogenated hydrocarbon.

In some embodiments, the electrochemical devices and methods described herein include an aqueous medium containing more than 5 wt.% Water. In some embodiments, the aqueous medium comprises more than 5 wt.% Water, or more than 6 wt.%, Or more than 8 wt.% Water, or more than 10 wt.% Water, or more than 15 wt.% Water, or more than 20 wt.% water, or more than 25 wt.% water, or more than 50 wt.% water, or more than 60 wt.% water, or more than 70 wt.% water, or more than 80 wt.% water, or more than 90 wt.% water, or about 99 wt.% water, or from 5 to 100 wt.% water, or from 5 to 99 wt.% water, or from 5 to 90 wt.% water, or from 5 to 80 wt.% water, or from 5 to 70 wt.% Water, or from 5 to 60 wt.% Water, or from 5

- 45,024,710 to 50 wt.% Water, or from 5 to 40 wt.% Water, or from 5 to 30 wt.% Water, or from 5 to 20 wt.% Water, or from 5 to 10 wt.% Water, or from 6 to 100 wt.% water, or from 6 to 99 wt.% water% or from 6 to 90 wt.% water, or from 6 to 80 wt.% water, or from 6 to 70 wt.% water, or from 6 to 60 wt.% water, or from 6 to 50 wt.% water, or from 6 to 40 wt.% water, or from 6 to 30 wt.% water, or from 6 to 20 wt.% water, or from 6 to 10 wt.% water, or from 8 to 100 wt.% water, or from 8 to 99 wt.% water, or from 8 to 90 wt.% water, or from 8 to 80 wt.% water, or from 8 to 70 wt.% water, or from 8 to 60 wt.% water, or from 8 to 50 wt.% water, or from 8 to 40 wt.% water, or from 8 d about 30 wt.% water, or from 8 to 20 wt.% water, or from 8 to 10 wt.% water, or from 10 to 100 wt.% water, or from 10 to 75 wt.% water, or from 10 up to 50 wt.% water, or from 20 to 100 wt.% water, or from 20 to 50 wt.% water, or from 50 to 100 wt.% water, or from 50 to 75 wt.% water, or from 50 up to 60 wt.% water, or from 70 to 100 wt.% water, or from 70 to 90 wt.% water, or from 80 to 100 wt.% water. In some embodiments, the aqueous medium may include a water soluble organic solvent.

In some embodiments of the methods and devices described herein, the total amount of metal ion in the anolyte or the amount of copper in the anolyte or the amount of iron in the anolyte or the amount of chromium in the anolyte or the amount of tin in the anolyte or the amount of platinum or the amount of metal ion that is in contact with an unsaturated or saturated hydrocarbon, is from 1 to 12 M, or from 1 to 11 M, or from 1 to 10 M, or from 1 to 9 M, or from 1 to 8 M, or from 1 to 7 M, or 1 to 6 M, or 1 to 5 M, or 1 to 4 M, or 1 to 3 M, or 1 to 2 M, or 2 to 12 M, or 2 to 11 M, or from 2 to 10 M, or from 2 to 9 M, or from 2 to 8 M, or from 2 to 7 M, or from 2 to 6 M, or from 2 to 5 M, or from 2 up to 4 M, or from 2 to 3 M, or from 3 to 12 M, or from 3 to 11 M, or from 3 to 10 M, or from 3 to 9 M, or from 3 to 8 M, or from 3 to 7 M, or from 3 to 6 M, or from 3 to 5 M, or from 3 to 4 M, or from 4 to 12 M, or from 4 to 11 M, or from 4 to 10 M, or from 4 to 9 M, or from 4 to 8 M, or from 4 to 7 M, or from 4 to 6 M, or from 4 to 5 M, or from 5 to 12 M, or from 5 to 11 M, or from 5 to 10 M or from 5 to 9 M, or from 5 to 8 M, or from 5 to 7 M, or from 5 to 6 M, or from 6 to 12 M, or from 6 to 11 M, or from 6 to 10 M, or from 6 to 9 M, or from 6 to 8 M, or from 6 to 7 M, or from 7 to 12 or from 7 to 11 M, or from 7 to 10 M, or from 7 to 9 M, or from 7 to 8 M, or from 8 to 12 M, or from 8 to 11 M, or from 8 to 10 M, or from 8 to 9 M, or from 9 to 12 M, or from 9 to 11 M, or from 9 to 10 M, or from 10 to 12 M, or from 10 to 11 M, or from 11 to 12 M. in some embodiments, the total amount of metal ion in the anolyte, as described above, is the amount of metal ion in the lower oxidation state plus the amount of metal ion in the higher oxidation state, or the total amount of metal ion in the higher oxidation state, or the total amount of metal ion in lower st degree of oxidation.

In some embodiments of the methods and devices described herein, an anolyte containing a metal ion may comprise a mixture of a metal ion of a lower oxidation state and a metal ion of a higher oxidation state. In some embodiments, it may be desirable to have in the anolyte a mixture of a metal ion at a lower oxidation state and a metal ion at a higher oxidation state. In some embodiments, the anolyte that is contacted with an unsaturated or saturated hydrocarbon contains a metal ion in a lower oxidation state and a metal ion in a higher oxidation state. In some embodiments, a metal ion of a lower oxidation state and a metal ion of a higher oxidation state are present in such a ratio that the metal ion reacts with an unsaturated or saturated hydrocarbon to form a halogenated or sulfonated hydrocarbon. In some embodiments, the ratio of the metal ion in the higher oxidation state to the metal ion in the lower oxidation state is from 20: 1 to 1:20, or from 14: 1 to 1: 2, or from 14: 1 to 8: 1, or from 14: 1 to 7: 1, or from 2: 1 to 1: 2, or from 1: 1 to 1: 2, or from 4: 1 to 1: 2, or from 7: 1 to 1: 2.

In some embodiments of the methods and devices described herein, the anolyte in the electrochemical devices and methods of this invention contains a metal ion in a higher oxidation state in the range of 4 to 7 M, a metal ion in a lower oxidation state in the range of 0.1 up to 2 M and sodium chloride in the range from 1 to 3 M. Anolyte may contain from 0.01 to 0.1 M hydrochloric acid. In some embodiments of the methods and devices described herein, anolyte reacting with hydrogen gas or with an unsaturated or saturated hydrocarbon contains a metal ion in a higher oxidation state in the range of 4 to 7 M, a metal ion in a lower oxidation state in the range from 0.1 to 2 M and sodium chloride in the range from 1 to 3 M. The anolyte may contain from 0.01 to 0.1 M hydrochloric acid.

In some embodiments of the methods and devices described herein, the anolyte may contain another cation, in addition to a metal ion. Another cation includes, but is not limited to, alkali metal ions and / or alkaline earth metal ions, for example, but not limited to, lithium, sodium, calcium, magnesium, etc. The content of another cation added to the anolyte may be from 0.01 to 5 M or from 0.01 to 1 M or from 0.05 to 1 M or from 0.5 to 2 M or from 1 to 5 M.

In some embodiments of the methods and devices described herein, the anolyte may contain acid. Acid can be added to the anolyte to bring the pH of the anolyte to 1 or 2 or less. The acid may be hydrochloric or sulfuric acid.

The devices provided in the text of this description include a reactor functionally connected to the 46,047,710 anode compartment. The reactor is configured to bring metal chloride contained in the anolyte into contact with hydrogen gas or an unsaturated or saturated hydrocarbon. The reactor may be any means of contacting the metal chloride contained in the anolyte with hydrogen gas or an unsaturated or saturated hydrocarbon. Such means or such a reactor are well known in the art and include, but are not limited to, pipes, channels, tanks, series of containers, containers, columns, pipelines, and the like. Some examples of such reactors are shown in FIG. 7A, 7B, 10A and 10B. The reactor may be equipped with one or more control units for monitoring temperature sensors, pressure sensors, control mechanisms, inert gas injectors, etc., in order to monitor, control and / or facilitate the reaction. In some embodiments, a reaction between a metal chloride in which the metal is in a higher oxidation state and an unsaturated or saturated hydrocarbon is carried out in a reactor at a temperature of from 100 to 200 ° C or from 100 to 175 ° C or from 150 to 175 ° C and pressure 0.7-3.4 MPa (100-500 psi), or 0.7-2.8 MPa (100-400 psi), or 0.7-2.1 MPa (100 -300 psi), or 1.0-2.4 MPa (150-350 psi). In some embodiments, the reactor components are lined with Teflon to prevent corrosion of these components. Some examples of reactors for reacting a metal of a higher oxidation state with hydrogen gas are illustrated in FIG. 7A and 7B.

In some embodiments, the unsaturated and saturated hydrocarbon can be controlledly directed to the anode compartment, where a metal oxidized halide or sulfate reacts with the unsaturated or saturated hydrocarbon to form the corresponding products inside the anode compartment. In some embodiments, the unsaturated or saturated hydrocarbon can be controlled to be directed to the anode compartment, where a metal chloride or a higher oxidation state reacts with the unsaturated or saturated hydrocarbon to form a chlorinated hydrocarbon. Such devices include an unsaturated or saturated hydrocarbon supply system that is operatively connected to the anode compartment and configured to supply an unsaturated or saturated hydrocarbon to the anode compartment. The unsaturated or saturated hydrocarbon may be a solid, liquid or gas. Unsaturated or saturated hydrocarbon can be fed to the anode using any means of transferring the unsaturated or saturated hydrocarbon from an external source to the anode compartment. Such means for conveying an unsaturated or saturated hydrocarbon from an external source to the anode compartment, or a system for supplying an unsaturated or saturated hydrocarbon, are well known in the art and include, but are not limited to, pipes, tanks, channels, pipelines, and the like. In some embodiments, a device or system for feeding unsaturated or saturated hydrocarbons includes a conduit that directs the unsaturated or saturated hydrocarbon from an external source to the anode. It should be understood that unsaturated or saturated hydrocarbon can be directed to the anode from the bottom of the cell, from the top of the cell or from the side. In some embodiments, an unsaturated or saturated gaseous hydrocarbon is directed to the anode so that the unsaturated or saturated gaseous hydrocarbon is not in direct contact with the anolyte. In some embodiments, an unsaturated or saturated hydrocarbon can be routed to the anode through multiple inlets. A source of an unsaturated or saturated hydrocarbon that provides an unsaturated or saturated hydrocarbon to the anode compartment in the methods and devices provided in the text of this description includes any source of unsaturated or saturated hydrocarbon known in the art. Such sources include, without limitation, commercially available unsaturated or saturated hydrocarbons and / or plants for producing unsaturated or saturated hydrocarbons, for example, petrochemical plants.

In some embodiments, methods and devices are provided in which the electrochemical cells of the present invention are mounted at the site of production of an unsaturated or saturated hydrocarbon, for example, in a refinery, for halogenation, for example, chlorination, unsaturated or saturated hydrocarbon. In some embodiments, the metal ion containing anolyte from an electrochemical device is transported to a refinery where an unsaturated or saturated hydrocarbon is produced to conduct halogenation, for example, chlorination, an unsaturated or saturated hydrocarbon. In some embodiments of the methods and devices of this invention, ethylene gas from refineries can be used without the need for filtration or purification of ethylene gas. Typically, ethylene gas plants clean the gas in a scrubber to remove impurities. In some embodiments of the methods and devices of this invention, such a preliminary gas purification in a scrubber is not necessary and can be avoided.

In some embodiments, metal production and halogenation processes, for example, a chlorination reaction, occur in the same anode compartment. An illustrative example of such an embodiment is shown in FIG. 9. It should be understood that the device 900 shown in FIG. 9 is shown for illustrative purposes only, and other metal ions of other oxidation states, other unsaturated or saturated hydrocarbons, other

- 47 024710 electrochemical devices in the cathode compartment of which products other than alkali are formed, for example, water or hydrogen gas, as well as other unsaturated or saturated gaseous hydrocarbons. In some embodiments, as illustrated in FIG. 9, the electrochemical device 900 includes an anode located near the AOM. Device 900 also includes a gas diffusion layer (GDS). The anolyte is in contact with the anode on one side and with the GDS on the other side. In some embodiments, the anode may be positioned so as to minimize anolyte resistance; for example, the anode can be located near the AOM or border with the AOM. In some embodiments, the anode converts metal ions from a lower oxidation state to a higher oxidation state. For example, the anode converts metal ions from an oxidation state of 1+ to an oxidation state of 2+. Cu ² + ions together with chloride ions to form SiS1 _2. Gaseous ethylene is compressed in a gas chamber on one side of the GDS. Ethylene gas then diffuses through the gas diffusion layer and reacts with a higher oxidation state of the metal chloride to form a chlorinated hydrocarbon, such as ethylene dichloride. In turn, the metal chloride CuCl ₂ is reduced to a lower oxidation state to form CuCl. In some embodiments, the anolyte can be selected and ethylene dichloride can be separated from the anolyte using separation techniques well known in the art, including, but not limited to, the use of filtration, vacuum distillation, fractional distillation, fractional crystallization, ion exchange resin, etc. In some embodiments, ethylene dichloride may have a higher density than the anolyte, and may form a separate layer inside the anode compartment. In such embodiments, ethylene dichloride can be removed from the bottom of the cell. In some embodiments, the gas chamber on one side of the GDS may have an outlet for removing gas. In some embodiments, the anode compartment may have an outlet for removing gaseous ethylene or gaseous by-products. Device 900 also includes an oxygen depolarization cathode that produces hydroxide ions from water and oxygen. Hydroxide ions can participate in any of the carbonate precipitation processes described in this text. In some embodiments, the cathode is not a gas diffusion cathode, but is the cathode described in FIG. 4A or 4B. In some embodiments, device 900 can be applied to any electrochemical device that produces alkali.

In some embodiments of the devices and methods described herein, no gas is generated at the cathode. In some embodiments of the devices and methods described herein, hydrogen gas is generated at the cathode. In some embodiments of the devices and methods described herein, no gas is generated at the anode. In some embodiments of the devices and methods described herein, no other gas is used on the anode other than a gaseous unsaturated or saturated hydrocarbon.

Another illustrative example of a reactor connected to an electrochemical device is shown in FIG. 10A. As illustrated in FIG. 10A, the anode compartment of the electrochemical device (the electrochemical device may be any electrochemical device described herein) is connected to a reactor, which is also connected to a source of unsaturated or saturated hydrocarbon; in FIG. 10A, an example is illustrated by ethylene (C ₂ H ₄ ). In some embodiments, the electrochemical device and the reactor are located inside the same unit and are connected inside this unit. An anolyte containing a metal ion in a higher oxidation state, possibly together with a metal ion in a lower oxidation state, is fed, together with ethylene, into a prestressed (e.g. lined with refractory layer) reactor. Ethylene chlorination occurs inside the reactor with the formation of ethylene dichloride (EDC) (or dichloroethane (DCE)) and a metal ion in a lower oxidation state. The reactor can operate in the range of 171-182 ° C (340 360 ° P) and 1.4-2.1 MPa (200-300 psi). To ensure operation with high selectivity in the reactor, other conditions can be specified, such as (but not limited to) the concentration of the metal ion, the ratio of the metal ion in the lower oxidation state to the metal ion in the higher oxidation state, partial pressures of DCE and water vapor. The heat of reaction can be removed by evaporation of water. In some embodiments, a cooling surface may not be required in the reactor, and thus, temperature gradients or strict temperature control may not be required. The gases leaving the reactor can be quickly cooled with water in a pre-stressed (e.g. lined with refractory layer) packing column (as shown in FIG. 10A as quick cooling). The liquid leaving the column can be further cooled and separated into the aqueous phase and the DCE phase. The aqueous phase can be separated, and part of it is recycled to the column as cooling water, and the remaining part can be recycled to the reactor or to an electrochemical device. The DCE product can be further cooled and evaporated quickly to separate more water and dissolved ethylene. This dissolved ethylene can be recycled as shown in FIG. 10A. Non-condensed gases from the cooling column can be recycled to the reactor, with the exception of the purge stream to remove inert substances. The purge stream may pass through an ethylene recovery device in order to keep the overall ethylene utilization ratio high, for example 95%. It is possible to conduct an experimental determination of the flammability limits of gaseous ethylene at actual operating temperatures, pressures and compositions. The structural material of the installation may include a prestressed refractory lining,

- 48,024,710

Na81ea11ou B and C, Inconel, titanium with dopants (e.g. AKOT, Ogabe II), tantalum, polyvinylidene fluoride (Kupag), Teflon, polyetheretherketone (PEEK), glass or other polymers or plastics. The reactor can also be designed so that the anolyte continuously flows into and out of the reactor.

Another illustrative example of a reactor connected to an electrochemical device is shown in FIG. 10B. As shown in FIG. 10B, the reactor device 1000 is a glass container A suspended on top of a metal flange B connected to an outlet line C by means of a metal ball coupling welded to the top of the flange. The glass reactor is enclosed in a metal shell Ό heated by electricity. Heat input and temperature can be controlled by an automatic temperature controller. The hydrocarbon can be introduced into the metal shell through the hole E and through the glass tube P, the lower part of which is closed by a porous glass filter. Such a scheme can provide pressure equalization on both sides of the glass reactor. The hydrocarbon can come into contact with a solution of a metal (a metal with a higher oxidation state) located at the bottom of the reactor, and can bubble through this medium. Volatile products, water vapor and / or unreacted hydrocarbon may exit via line C, which can be equipped with valve H, which can reduce pressure to atmospheric pressure. Exhaust gases can pass through an appropriate trapping system to remove the product. The device can also be equipped with a bypass O, which allows the gas to pass through the pressure zone without passing through the medium of an aqueous metal solution. In some embodiments, the reduced lower oxidation metal ions that remain in the vessel are electrolyzed as described herein to regenerate the higher oxidation metal ions.

An illustrative embodiment of the present invention is shown in FIG. 11. As illustrated in FIG. 11, the electrochemical device 600 shown in FIG. 6 (or, alternatively, the device 400 depicted in FIG. 4A) can be combined with the electrochemical device 1100 CuCl-HC1 (also illustrated as the device in FIG. 4B). In the electrochemical device 1100 CuC1-HC1, CuC1 and HC1 are fed to the anode, which leads to the formation of CuC1 ₂ and hydrogen ions. Hydrogen ions pass through a proton-exchange membrane to the cathode, where hydrogen gas is formed. Chloride-transmitting membranes may also be used in some embodiments. In some embodiments, it is contemplated that the CuCl-HC1 cell may operate at a voltage of 0.5 V or less, and the device 600 may operate at a voltage of 0 V or less. Due to losses due to resistance, the voltage may be somewhat different from the expected voltage.

In one aspect of the devices and methods provided in the text of this description, CuCl ₂ formed in the anolyte can be used to produce copper. For example, CuCl ₂ obtained in the devices and methods of this invention can be used for the leaching process in the extraction of copper from copper minerals. Just as an example, a mineral that can be leached in a chloride environment by using an oxidant, Cu + ² is chalcopyrite. Bivalent copper can leach copper from their chalcopyrite and other sulfides. After the copper is leached, other minerals such as iron, sulfur, gold, silver, etc. can be extracted. In some embodiments, CuC12 obtained using the electrochemical cell described herein can be added to a copper mineral concentrate. Cu + ² ions may oxidize copper mineral and forming SiS1. The CuCl solution obtained from the concentrate can be fed back to the anode compartment of the electrochemical cell described in this text, where CuCl can be converted to CuCl12. Then CuCl ₂ can be fed back to the mineral concentrate for further oxidation of the copper mineral. After the copper is leached, silver can be carburized, along with additional precipitation of zinc, lead, etc. Then, copper can be precipitated as copper oxide by treatment with alkali; while alkali can be obtained in the cathode compartment of the electrochemical cell. After deposition of copper in the form of oxide, the filtrate ΝαΟ can be returned to the electrochemical cell. Hydrogen gas obtained at the cathode can be used to reduce copper oxide to produce metallic copper (at high temperature). Then, copper products, such as a rod for producing copper wire, can be cast from molten copper. This method can be used for low-grade ores or for various types of copper minerals. The electrochemical installation can be located near the quarry or near the concentration plant, which eliminates the cost of transporting waste and allows you to transport only products of value, i.e. metal.

The methods and devices described herein may be batch methods or devices or continuous stream methods or devices.

The reaction of gaseous hydrogen or an unsaturated or saturated hydrocarbon with a metal ion in a higher oxidation state, as described herein in aspects and embodiments, is carried out in an aqueous medium. In some embodiments, such a reaction may occur in a non-aqueous liquid medium, which may be a solvent for the feedstock — a hydrocarbon or hydrogen gas. The liquid medium or solvent may be aqueous or non-aqueous. Suitable non-aqueous solvents are polar and non-polar aprotic solvents, for example dimethylform 49 49 0 710 mid (DMF), dimethyl sulfoxide (DMSO), halogenated hydrocarbons, for example dichloromethane, carbon tetrachloride and 1,2-dichloroethane, and organic nitriles, for example acetonitrile. Organic solvents may contain a nitrogen atom capable of forming a chemical bond with a metal in a lower oxidation state, and thus give increased stability to a metal ion in a lower oxidation state. In some embodiments, the organic solvent is acetonitrile.

In some embodiments, if the organic solvent is used to react the metal ion with a higher oxidation state with hydrogen gas or a hydrocarbon, it may be necessary to remove water from the metal containing medium. As such, the metal ion obtained from the electrochemical device described herein may contain water. In some embodiments, water can be removed from a medium containing a metal ion by azeotropic distillation of the mixture. In some embodiments, a solvent containing a highly oxidized metal ion and hydrogen gas or an unsaturated or saturated hydrocarbon may contain 5-90 wt.%, Or 5-80 wt.%, Or 5-70 wt.%, Or 5- 60 wt.%, Or 5-50 wt.%, Or 5-40 wt.%, Or 5-30 wt.%, Or 5-20 wt.%, Or 5-10 wt.%, Water in the reaction medium. The amount of water that is acceptable in the reaction medium may depend on the particular halide carrier in the medium; for example, the allowable amount of water for copper chloride (11) will be greater than for iron chloride (111). Such azeotropic distillation can be avoided if an aqueous medium is used in the reactions.

In some embodiments, the reaction of the metal ion in a higher oxidation state with hydrogen gas or an unsaturated or saturated hydrocarbon can occur at a reaction temperature of from 50 to 350 ° C. In an aqueous medium, the reaction can be carried out at a pressure above atmospheric, up to 6.9 MPa (1000 psi) or less, in order to maintain the reaction medium in the liquid phase at a temperature of from 50 to 200 ° C., usually from about 120 to about 180 ° C.

In some embodiments, the reaction of the metal ion to a higher oxidation state with an unsaturated or saturated hydrocarbon may include a halide carrier. In some embodiments, the ratio of metal halide to total metal ion in the higher oxidation state is 1: 1; or more than 1: 1; or 1.5: 1; or more than 2: 1; or at least 3: 1. Thus, for example, this ratio in solutions of copper halide (11) in concentrated hydrochloric acid can be approximately 2: 1 or 3: 1. In some embodiments, due to the high rate of use of the halide support, it may be desirable to use high concentration metal halides and apply saturated or near-saturated metal halide solutions. If desired, solutions can be buffered to maintain pH at the desired level during the halogenation reaction.

In some embodiments, a non-halide metal salt can be added to a solution containing a metal with a higher oxidation state. The added salt may be soluble in the metal halide solution. Examples of suitable salts for incorporation into solutions of copper chloride (11) include, but are not limited to, copper sulfate, copper nitrate, and copper tetrafluoroborate. In some embodiments, a metal halide other than the metal halide used in these methods and devices can be added. For example, iron (111) chloride can be added to systems with copper chloride (11) during the halogenation of an unsaturated hydrocarbon.

The feed — an unsaturated or saturated hydrocarbon — can be fed continuously or periodically to the halogenation vessel. Effective halogenation may depend on achieving close contact between the feed and the metal ion in the solution; and the halogenation reaction can be carried out by a method selected to increase or maximize such contact. The metal ion solution can be shaken by stirring or shaking, or by any method desired, for example, the reaction can be carried out in a column, for example, in a packed column, or in an irrigated bed reactor, or in the reactors described herein. For example, if the unsaturated or saturated hydrocarbon is gaseous, a counterflow technique can be used in which an unsaturated or saturated hydrocarbon is passed through a column or reactor from bottom to top and a solution of a metal ion is passed through a column or reactor from top to bottom. In addition to improving the contact of an unsaturated or saturated hydrocarbon and a metal ion in a solution, the technology described here can also increase the dissolution rate of an unsaturated or saturated hydrocarbon in a solution, which may be desirable when the solution is aqueous and the solubility of an unsaturated or saturated hydrocarbon in water is low. Dissolution of raw materials can also contribute to increased pressure.

Mixtures of saturated, unsaturated hydrocarbons and / or partially halogenated hydrocarbons may be used. In some embodiments, the partially halogenated products of the process of this invention that are capable of further halogenation can be recycled to the reaction vessel through a product recovery step, and, if appropriate, through a lower oxidation rate of the metal ion regeneration. In some embodiments, the halogenation reaction can be continued outside the vessel for carrying out the halogenation reaction, for example, in a separate regeneration vessel, and the reaction should be carefully monitored to avoid excessive

- 50,047,710 halogenating an unsaturated or saturated hydrocarbon.

In some embodiments, the electrochemical devices described herein are arranged adjacent to a plant producing an unsaturated or saturated hydrocarbon, or producing hydrogen gas. In some embodiments, the electrochemical devices described herein are installed adjacent to a PVC manufacturing facility. For example, in some embodiments, an electrochemical device is within a radius of 100 miles of a plant for producing gaseous ethylene, gaseous hydrogen, vinyl chloride monomer and / or PVC. In some embodiments, the electrochemical devices described herein are installed inside or outside an ethylene plant to react ethylene with a metal ion. In some embodiments, the devices described above are modified using the electrochemical devices described herein. In some embodiments, the anolyte containing a metal ion of a higher oxidation state is transported to the location of the plants described above. In some embodiments, an anolyte containing a higher oxidation metal ion is transported, within 100 miles, to the location of the facilities described above. In some embodiments, the electrochemical devices described herein are located near the plants described above, as well as near the source of divalent cations, so as to react the alkali obtained in the catholyte with divalent cations to form carbonate / bicarbonate products. In some embodiments, the electrochemical devices described herein are located near the plants described above, near a source of divalent cations and / or a source of carbon dioxide, so that carbon dioxide can be isolated with alkali obtained in catholyte to form carbonate / bicarbonate products. In some embodiments, carbon dioxide obtained from a refinery that produces an unsaturated or saturated hydrocarbon is used in electrochemical devices or used to precipitate carbonate / bicarbonate products. Accordingly, in some embodiments, the electrochemical devices described herein are located near the facilities described above, near the source of divalent cations and / or the source of carbon dioxide, for example, refineries producing unsaturated or saturated hydrocarbons, so that carbon dioxide can be isolated with alkali obtained in catholyte , with the formation of carbonate / bicarbonate products.

By reacting the metal chloride to a higher oxidation state with unsaturated or saturated hydrocarbons described herein, any amount of halogenated or sulfonated hydrocarbons can be obtained. Chlorinated hydrocarbons can be used in the chemical and / or manufacturing industries. Chlorinated hydrocarbons can be used as chemical intermediates or solvents. The use of solvents includes a wide variety of applications, including the purification of metals and fabrics, the extraction of fats and oils and the use as a reaction medium for chemical syntheses.

In some embodiments, an unsaturated hydrocarbon, such as ethylene, reacts with a higher oxidation state of metal chloride to produce ethylene dichloride. Ethylene dichloride can be used for a number of purposes, including, but not limited to, the production of chemicals included in plastics, rubber and synthetic fabric fibers, for example, but not limited to vinyl chloride, tri- and tetrachlorethylene, vinylidene chloride, trichloroethane, ethylene glycol, diaminoethylene, polyvinyl chloride , nylon, rayon, styrene butadiene rubber and various plastics; as a solvent used for degreasing and for removing paint; as a solvent for resins, asphalt, bitumen, rubber, fats, oils, waxes, gums, in photography, photocopying, cosmetics, medicines and for cleaning the skin; fumigants for grain, means for pollinating fruit trees, removing fungi in houses, processing upholstery materials and carpets; as a reagent for etching; as a reagent for wall blocks; as an intermediate in the preparation of various organic compounds, such as ethylenediamine; as a source of chlorine with the elimination of ethene and chloride; as a precursor for 1,1,1 trichloroethane, which is used for dry cleaning; as an anti-knock additive in leaded fuels; it is used in the extraction of spices such as annatto, paprika and turmeric; as a diluent for pesticides; in paints, coatings and adhesives; and in their combinations.

In the methods and devices described herein, in some embodiments, hydrochloric acid is not formed in the anode compartment. In the methods and devices described herein, in some embodiments, no gas is formed on the anode. In the methods and devices described herein, in some embodiments, no gas is used at the anode. In the methods and devices described herein, in some embodiments, hydrogen gas is formed at the cathode. In the methods and devices described herein, in some embodiments, hydrogen gas is not formed at the cathode.

In some embodiments, the cathode and anode are wired so that current flows through the cell. In such embodiments, the cell can act as a current source, and the current generated in the cell can be used to produce alkali that is taken from the cell. In some embodiments, the cell resistance may increase, and the current may decrease. In such embodiments to the electrochemical

- 51 024710 cells can be applied voltage. Cell resistance can increase for various reasons, including, but not limited to, electrode corrosion, solution resistance, clogging of the membrane, etc. In some embodiments, the current can be diverted from the cell using a current load.

In some embodiments, the devices provided in the text of this description, lead to a reduction to zero of the voltage in the devices that produce alkali, compared with the chlor-alkali process or chlor-alkali process with QCD or any other process in which metal ions are oxidized in the anode compartment from a lower degree oxidation to a higher oxidation state. In some embodiments, the devices described herein operate at a voltage of less than 2 V, or less than 1.2 V, or less than 1.1 V, or less than 1 V, or less than 0.9 V, or less than 0.8 V, or less than 0, 7 V, or less than 0.6 V, or less than 0.5 V, or less than 0.4 V, or less than 0.3 V, or less than 0.2 V, or less than 0.1 V, or at 0 V, or from 0 to 1.2 V, or from 0 to 1 V, or from 0 to 0.5 V, or from 0.5 to 1 V, or from 0.5 to 2 V, or from 0 to 0.1 V, or from 0.1 to 1 V, or from 0.1 to 2 V, or from 0.01 to 0.5 V, or from 0.01 to 1.2 V, or from 1 to 1.2 V , or from 0.2 to 1 V, or at 0 V, or 0.5 V, or 0.6 V, or 0.7 V, or 0.8 V, or 0.9 V, or 1 V.

The term voltage used in the text of this description includes the voltage or bias voltage applied to the electrochemical cell or taken from the electrochemical cell, which provides the desired reaction between the anode and cathode in the electrochemical cell. In some embodiments, the desired reaction may be electron transfer between the anode and cathode, so that an alkaline solution, water or hydrogen gas is formed in the catholyte, and a metal ion is oxidized on the anode. In some embodiments, the desired reaction may be electron transfer between the anode and cathode, such that a metal ion of a higher oxidation state from a metal ion of a lower oxidation state forms in the anolyte. The voltage can be applied to the electrochemical cell using any means of supplying current between the anode and cathode of the electrochemical cell. Such means are well known in the art and include, without limitation, devices such as a battery, a fuel cell, a sunlight-powered device, a wind-driven device, and combinations thereof. The type of electrical energy source for providing current may be any energy source known to those skilled in the art. For example, in some embodiments, voltage can be applied by attaching the anodes and cathodes of the cell to an external DC source (IC). The energy source may be a source of alternating current (AC), rectified to direct current. The direct current source may have a voltage and current regulator to supply the necessary voltage value to the electrochemical cell.

In some embodiments, the current applied to the electrochemical cell is at least 50 mA / cm ² , or at least 100 mA / cm ² , or at least 150 mA / cm ² , or at least 200 mA / cm ² , or at least 500 mA / cm ² , or at least 1000 mA / cm ² , or at least 1500 mA / cm ² , or at least 2000 mA / cm ² , or at least 2500 mA / cm ² , or from 100 to 2500 mA / cm ² , or from 100 to 2000 mA / cm ² , or from 100 to 1500 mA / cm ² , or from 100 to 1000 mA / cm ² , or from 100 to 500 mA / cm ² , or from 200 to 2500 mA / cm ^2, or from 200 to 2000 mA / cm ^2, or from 200 to 1500 mA / cm ^2, or from 200 to 1000 mA / cm ^2, or 200 to 500 mA / cm ^2, or from 500 to 2500 mA / cm ^2, or from 500 to 2000 mA / cm ^2, or from 500 to 1500 mA / cm ^2, or from 500 to 1000 mA / cm ^2, or 1000 to 2500 mA / cm ² , or from 1000 to 2000 mA / cm ² , or from 1000 to 1500 mA / cm ² , or from 1500 to 2500 mA / cm ² , or from 1500 to 2000 mA / cm ² , or 2000 to 2500 mA / cm ² .

In some embodiments, the cell operates at a voltage of 0 to 3 V, with a current of 100 to 250 mA / cm ² , or 100 to 150 mA / cm ² , or 100 to 200 mA / cm ² , or 100 to 300 mA / cm ² , or from 100 to 400 mA / cm ² , or from 100 to 500 mA / cm ² , or from 150 to 200 mA / cm ² , or from 200 to 150 mA / cm ² , or from 200 to 300 mA / cm ² , or 200 to 400 mA / cm ² , or 200 to 500 mA / cm ² , or 150 mA / cm ² , or 200 mA / cm ² , or 300 mA / cm ² , or 400 mA / cm ² , or 500 mA / cm ² , or 600 mA / cm ² . In some embodiments, the cell operates at a voltage of 0 to 1 V. In some embodiments, the cell operates at a voltage of 0 to 1.5 V, when a current of 100 to 250 mA / cm ² , or 100 to 150 mA / cm ² , is applied. or from 150 to 200 mA / cm ² , or 150 mA / cm ² , or 200 mA / cm ² . In some embodiments, the cell operates at a voltage of 0 to 1 V, at a current load of 100 to 250 mA / cm ² , or 100 to 150 mA / cm ² , or 150 to 200 mA / cm ² , or 150 mA / cm ² , or 200 mA / cm ² . In some embodiments, the cell operates at a voltage of 0.5 V at a current or current load of 100 to 250 mA / cm ² , or 100 to 150 mA / cm ² , or 150 to 200 mA / cm ² , or 150 mA / cm ² , or 200 mA / cm ² .

In some embodiments, the devices and methods provided herein further include a filter and / or gasket between the anode and the ion exchange membrane and / or between the cathode and the ion exchange membrane. Electrochemical devices containing filters and / or gaskets are described in provisional application for US patent No. 61/442573, registered February 14, 2011, which in its entirety is incorporated into this description by reference.

The devices described herein are applicable or can be used for any of the methods described in this text. In some embodiments, the devices provided herein further include an oxygen gas supply or supply system operably connected to the cathode compartment. The gaseous oxygen supply system is configured to supply gaseous 52 024710 different oxygen to the gas diffusion cathode. In some embodiments, the gaseous oxygen supply system is configured to deliver gas to a gas diffusion cathode, on which a catalytic reaction of gas reduction to hydroxide ions occurs. In some embodiments, gaseous oxygen and water are reduced to hydroxide ions; unreacted oxygen gas in the device is withdrawn and recycled to the cathode. Oxygen gas can be supplied to the cathode using any means of supplying oxygen gas from an external source to the cathode. Such means for supplying gaseous oxygen from an external source to the cathode, or a system for supplying gaseous oxygen, are well known in the art and include, but are not limited to, pipes, channels, pipelines, and the like. In some embodiments, the oxygen gas supply device or system includes a channel that directs oxygen gas from an external source to the cathode. It should be understood that gaseous oxygen can be directed to the cathode from the bottom of the cell, from the top of the cell or from the side. In some embodiments, gaseous oxygen is directed to the back of the cathode, where gaseous oxygen does not directly contact the catholyte. In some embodiments, gaseous oxygen can be directed to the cathode through multiple inlets. An oxygen source that delivers gaseous oxygen to the gas diffusion cathode in the methods and devices provided herein will include any oxygen source known in the art. Such sources include, but are not limited to, atmospheric air; commercially available gaseous oxygen in cylinders; gaseous oxygen obtained by fractional distillation of liquefied air; gaseous oxygen obtained by passing air through a layer of zeolites; gaseous oxygen obtained by electrolysis of water; oxygen obtained by passing air through ceramic membranes based on zirconia under the influence of either high pressure or electric current; chemical oxygen generators; gaseous oxygen obtained from liquid oxygen stored in insulated tanks; or a combination of these sources. In some embodiments, the oxygen source may also provide gaseous carbon dioxide. In some embodiments, oxygen from a gaseous oxygen source can be cleaned before being fed to the cathode compartment. In some embodiments, oxygen from a source of gaseous oxygen is used in the cathode compartment without pretreatment.

Alkali in the cathode compartment.

The catholyte containing alkali can be taken from the cathode compartment. The alkali can be separated from catholyte using methods known in the art, including, but not limited to, diffusion dialysis. In some embodiments, the alkali obtained using the methods and devices provided herein is used as is for commercial purposes or used in commercial processes known in the art. The purity of the alkali obtained using these methods and devices may vary depending on the requirements of the final application. For example, the methods and devices provided herein that utilize an electrochemical cell equipped with membranes can form an alkali having the quality obtained by membrane cleaning, which may be substantially free of impurities. In some embodiments, a less pure alkali can also be obtained without using membranes or adding carbon to the catholyte. In some embodiments, the alkali obtained in the catholyte has a concentration of more than 2 wt.%, Or more than 5 wt.%, Or from 5 to 50 wt.%.

In some embodiments, the alkali obtained in the cathode compartment can be used in various commercial processes, as described herein. In some embodiments, a device suitable for such use may be operatively connected to an electrochemical unit, or alkali may be transported to an appropriate location for use. In some embodiments, the device includes a collector configured to take alkali from the cathode compartment and supply it to an appropriate process, which may be any means of alkali collection and treatment, including, but not limited to, tanks, collectors, pipelines, and the like, which can collect, process and / or transport alkali obtained in the cathode compartment for use in various commercial processes.

In some embodiments, an alkali, for example sodium hydroxide, obtained in catholyte, is used commercially as it is, or processed in various ways well known in the art. For example, sodium hydroxide formed in catholyte can be used as a base in the chemical industry, in the household, and / or in the production of cellulose, paper, textiles, drinking water, soap, surfactants, and sewer pipe cleaners. In some embodiments, sodium hydroxide can be used in the manufacture of paper. Along with sodium sulfide, sodium hydroxide can be a component of the white liquor solution used to separate lignin from cellulose fibers in the Kraft process. It can also be useful in some later stages of the process of bleaching brown pulp obtained in the pulping process. These steps may include oxygen delignification, oxidative extraction, and simple extraction; all of these processes may require a strong alkaline environment with a pH> 10.5 at the end of the stage. In some embodiments, sodium hydroxide can be used to digest tissues. This process may include placing the carcass in a sealed chamber, followed by placing the carcass in a mixture of sodium hydroxide and water, which can break down the chemical bonds that maintain the integrity of the body. In some embodiments, sodium hydroxide can be used in the Bayer process, where sodium hydroxide is used in the refining of aluminum ores (bauxites) to produce alumina. Alumina is a raw material that can be used to produce aluminum metal using the Na11Negoi electrolytic method. Alumina can be dissolved in sodium hydroxide, leaving impurities that are less soluble at high pH, such as iron oxides, in the form of a highly alkaline red mud. In some embodiments, sodium hydroxide can be used in soap manufacturing processes. In some embodiments, sodium hydroxide can be used in a biodiesel manufacturing process in which sodium hydroxide can be used as a catalyst for transesterification of methanol and triglycerides. In some embodiments, sodium hydroxide can be used as a cleaning agent, for example, but not limited to, a degreasing agent for steel and glassware.

In some embodiments, sodium hydroxide can be used in cooking. The use of sodium hydroxide for cooking includes, but is not limited to, washing or chemically peeling fruits and vegetables, processing chocolate and cocoa, producing caramel colors, scalding poultry, producing soft drinks and thickening ice cream. Olives can be soaked in sodium hydroxide to soften them, while pretzels and German alkaline bagels can be glazed with sodium hydroxide solution before baking to make them crispy. In some embodiments, sodium hydroxide can be used in the household as a pipe cleaner, to clean clogged drains. In some embodiments, sodium hydroxide can be used as a straightener to straighten hair. In some embodiments, sodium hydroxide can be used in refineries and in oil drilling, as it can increase viscosity and prevent the deposition of heavy materials. In the chemical industry, sodium hydroxide can provide the functions of neutralizing acids, hydrolysis, condensation, saponification and substitution of other groups in organic compounds with hydroxyl ions. In some embodiments, sodium hydroxide can be used in the textile industry. Mercerization of the fiber with sodium hydroxide solution can provide higher tensile strength and give shine. It can also remove waxes and oils from the fiber to make the fiber more susceptible to bleaching and dyeing. Sodium hydroxide can also be used to produce viscose fiber. In some embodiments, sodium hydroxide can be used to produce sodium hypochlorite, which can be used as a bleach and disinfectant in the household; and to produce sodium phenolate, which can be used in antiseptics and for the production of aspirin.

Contact of carbon dioxide with catholyte.

In one aspect, as described herein, methods and devices are provided that include bringing carbon dioxide into contact with the catholyte either inside the cathode compartment or outside the cathode compartment. In one aspect, methods are provided comprising contacting the anode with a metal ion in the anolyte in the anode compartment; transfer or oxidation of a metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; getting alkali in catholyte; and bringing the alkali in the catholyte into contact with carbon from a carbon source, for example, carbon dioxide from a carbon dioxide source. In some embodiments, the methods further include using a higher oxidation metal formed in the anode compartment as prepared (as described herein) or using it to carry out a reaction with hydrogen gas or a reaction with unsaturated or saturated hydrocarbons (as described in this text). In some embodiments, a method is provided comprising contacting the anode with anolyte; oxidation of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; obtaining hydroxide ions in catholyte; and bringing the catholyte into contact with an industrial flue gas containing carbon dioxide or with a carbon dioxide solution containing bicarbonate ions.

In another aspect, devices are provided comprising an anode compartment comprising an anode in contact with a metal ion in an anolyte; wherein the anode is configured to transfer a metal ion from a lower oxidation state to a higher oxidation state; a cathode compartment including a cathode in contact with the catholyte, wherein the cathode is configured to produce alkali; and a contact apparatus operably connected to the cathode compartment and configured to bring carbon from a carbon source, for example, carbon dioxide from a carbon dioxide source, into contact with an alkali located in a catholyte. In some embodiments, the device further includes a reactor operably coupled to the anode compartment and configured to react the metal ion to a higher oxidation state with hydrogen gas or with unsaturated or saturated hydrocarbons (as described herein).

In some embodiments, carbon from a carbon source is treated with catholyte to obtain a solution of carbon dioxide dissolved in a catholyte alkali. The alkali present in the catholyte can facilitate the dissolution of carbon dioxide in the solution. The dissolved carbon dioxide solution includes carbonic acid, bicarbonate, carbonate, or any combination thereof. In such a method and apparatus, carbon from a carbon source includes gaseous carbon dioxide from an industrial process or a solution of carbon dioxide from a gas-liquid contactor that is in contact with gaseous carbon dioxide from an industrial process. Such a contact apparatus is further defined in the text of this description. In some embodiments of devices including a contact apparatus, the cathode compartment includes, in addition to hydroxide ions, bicarbonate and carbonate ions.

An illustrative example of an electrochemical device combined with carbon from a carbon source is illustrated in FIG. 12. It should be understood that the device 1200 shown in FIG. 12 is for illustrative purposes only; and other metal ions with other degrees of oxidation (for example, chromium, tin, etc.), other electrochemical devices described in this text, for example, electrochemical devices depicted in FIG. 1A, 1B, 2, 3A, 3B, 4A, 5A, 5C, 6, 8A, 8B, 9 and 11, and a third electrolyte other than sodium chloride, for example sodium sulfate, are variants that are equally applicable to this device. The electrochemical device 1200 shown in FIG. 12 includes an anode and a cathode separated by an anion exchange membrane and a cation exchange membrane, creating a third compartment containing a third electrolyte, NaCl. The metal ion is oxidized in the anode compartment from a lower oxidation state to a higher oxidation state; and the metal with a higher oxidation state is then used to carry out reactions in the reactor, for example, a reaction with hydrogen gas or a reaction with an unsaturated or saturated hydrocarbon. Products resulting from such reactions are described in this text. To illustrate in FIG. Figure 12 shows the cathode on which hydrogen gas is generated, although the CCD is equally applicable to this device. The cathode compartment is connected to a gas-liquid contactor that is in contact with gaseous carbon dioxide. An alkali-containing catholyte, for example sodium hydroxide and / or sodium carbonate, is circulated through a gas-liquid contactor, which brings the catholyte into contact with carbon dioxide gas, resulting in a solution of sodium bicarbonate / sodium carbonate. This dissolved carbon dioxide solution is then circulated to the cathode compartment, where the alkali obtained at the cathode converts bicarbonate ions to carbonate ions, bringing the catholyte pH to below 12. This, in turn, reduces the cell voltage to below 2 V. sodium carbonate can be recycled back to the gas-liquid contactor for additional contact with gaseous carbon dioxide, or it can be selected for the process of deposition of calcium carbonate, as described in this text e. In some embodiments, gaseous carbon dioxide is sent directly to the cathode compartment, without intermediate use of a gas-liquid contactor. In some embodiments, the bicarbonate solution from the gas-liquid contactor is not sent to the cathode compartment, but is instead used to precipitate the bicarbonate product.

Methods and devices associated with bringing carbon from a carbon source into contact with a catholyte (if the cathode is a QCD or a cathode producing hydrogen gas), as described herein and illustrated in FIG. 12 can lead to a decrease in voltage compared to methods and devices in which carbon from the carbon source does not contact the catholyte. Reduced voltage, in turn, can lead to lower electricity consumption and lower carbon dioxide emissions when generating electricity. This can lead to greener chemicals, for example, sodium carbonate, sodium bicarbonate, bicarbonate or calcium / magnesium carbonate, halogenated hydrocarbons and / or acids, which are obtained using the efficient and energy-saving methods and devices of this invention. In some embodiments, an electrochemical cell in which carbon from a carbon source (e.g., carbon dioxide gas or a solution of sodium carbonate / bicarbonate from a gas-liquid contactor) is contacted with an alkali obtained at the cathode has a theoretical decrease in the voltage of the cathode half cell or a theoretical decrease in the total voltage of the cell above 0 , 1 V, or more than 0.2 V, or more than 0.5 V, or more than 1 V, or more than 1.5 V, or from 0.1 to 1.5 V, or from 0.1 to 1 V, or from 0.2 to 1.5 V, or from 0.2 to 1 V, or from 0.5 to 1.5 V, or from 0.5 to 1 V, compared with lektrohimicheskoy cell, wherein the carbon is not in contact with the caustic formed at the cathode, e.g., CCD or cathode, where hydrogen gas. In some embodiments, this stress reduction is achieved at a catholyte pH of from 7 to 13, or from 6 to 12, or from 7 to 12, or from 7 to 10, or from 6 to 13.

Based on the Nernst equation explained earlier, if a metal in a lower oxidation state is oxidized at the anode to a metal in a higher oxidation state as follows:

C ⁺ C ²⁺ + 2e

E of the _anode , depending on the concentration of copper ions (11), is 0.159-0.75 V.

If water is reduced at the cathode to hydroxide ions and hydrogen gas (as illustrated in FIG. 4A or FIG. 12), and the hydroxide ions come into contact with bicarbonate ions (for example, carbon dioxide gas dissolved directly in catholyte, or with a solution carbo- 55 024710 nata / sodium bicarbonate from a gas-liquid contactor directed to the catholyte) to produce carbonate, the pH of the catholyte decreases from 14 to less than 14, as follows:

Ekegoda = - 0.059 pH _k ; where the pH is the pH of catholyte = 10 Ekatoda “0.59

Then E _total . ranges from 0.749 to 1.29, depending on the concentration of copper ions in the anolyte. E _cathode = - 0.59 gives a voltage drop of more than 200 mV, or from 200 mV to 500 mV, or from 100 to 500 mV, with respect to E _cathode = - 0.83 for a cathode producing hydrogen gas that is not in contact with bicarbonate / carbonate ions. E _total = from 0.749 to 1.29 gives a voltage reduction of more than 200 mV, or from 200 mV to 1.2 V, or from 100 mV to 1.5 V, with respect to E _total . = 0.989 to 1.53 for a cathode producing hydrogen gas that is not in contact with bicarbonate / carbonate ions.

Similarly, if water is reduced to hydroxide ions in a CDC (as illustrated in FIG. 5A), and hydroxide ions are contacted with bicarbonate ions (e.g., carbon dioxide gas dissolved directly in catholyte, or with a solution of sodium carbonate / bicarbonate) from a gas-liquid contactor directed to the catholyte) to produce carbonate, the pH of the catholyte decreases from 14 to less than 14, as follows:

Ekatode ~ 1.224 - 0.059 pHk, where pH _k = 10 Ekatode ⁼ 0.636 V

Then E _total . ranges from -0.477 to 0.064 V, depending on the concentration of copper ions in the anolyte. E _cathode = 0.636 gives a voltage drop of more than 100 mV, or from 100 mV to 200 mV, or from 100 to 500 mV, or from 200 to 500 mV, with respect to E _cathode = 0.4 for a cathode with oxygen depolarization (QCD) which is not in contact with bicarbonate / carbonate ions. E _total = -0.477 to 0.064 V gives a voltage reduction of more than 200 mV, or from 200 mV to 1.2 V, or from 100 mV to 1.5 V, with respect to E _total . = -0.241 to 0.3 for KKD which is not in contact with bicarbonate / carbonate ions.

As described above, with an increase in the catholyte pH to 14 or higher, the difference between the potential of the anode half cell and the potential of the cathode half cell will increase. As the cell's operating time increases without adding CO ₂ or other effects, such as dilution with water, the required cell potential will continue to increase. The operation of an electrochemical cell with a pH at the cathode from 7 to 13 or from 7 to 12 provides significant energy savings.

Thus, at different pH values of catholyte, hydroxide ions, carbonate ions and / or bicarbonate ions are formed in catholyte if the voltage applied between the anode and cathode is less than 2.9, or less than 2.5, or less than 2, 1, or 2.0, or less than 1.5, or less than 1.0, or less than 0.5, or from 0.5 to 1.5 V, while the pH in the catholyte is from 7 to 13, or from 7 to 12, or from 7 to 10.

In some embodiments, the carbon source is any carbon dioxide gas source and / or any source that provides a dissolved form or carbon dioxide solution. The dissolved form of carbon dioxide or a solution of carbon dioxide includes carbonic acid, bicarbonate ions, carbonate ions, or a combination thereof. In some embodiments, gaseous oxygen and / or gaseous carbon dioxide supplied to the cathode originates from any oxygen source and a source of gaseous carbon dioxide known in the art. The source of gaseous oxygen and the source of gaseous carbon dioxide may be the same, or they may be different. Some examples of a source of gaseous oxygen and a source of gaseous carbon dioxide are described in this text.

In some embodiments, the alkali obtained in the cathode compartment can be treated with a gaseous stream of carbon dioxide and / or a dissolved form of carbon dioxide to obtain carbonate / bicarbonate products that can be used commercially as they are, or can be treated with bivalents cations, for example, but not limited to, alkaline earth metal ions, to produce alkaline earth metal carbonates and / or bicarbonates.

As used herein, the term carbon from a carbon source includes a gaseous form of carbon dioxide or a dissolved form or solution of carbon dioxide. Carbon from a carbon source includes CO ₂ , carbonic acid, bicarbonate ions, carbonate ions, or a combination thereof. As used herein, the term carbon source includes any source that provides a gaseous and / or dissolved form of carbon dioxide. Sources of carbon include, but are not limited to, effluent from manufacturing processes that provide a gaseous stream of CO2; a gas-liquid contactor that provides a solution containing CO2, carbonic acid, bicarbonate ions, carbonate ions, or a combination thereof; and / or bicarbonate saline.

In some embodiments, gaseous CO ₂ is an effluent or a product of an industrial plant. In these embodiments, the nature of the industrial installation may vary. Industrial plants include, but are not limited to, refineries that produce unsaturated or saturated hydrocarbons; power plants (56 024 710 For instance the measures as described in detail in International Application PCT / I808 / 88318, entitled £ eesschee1egshd Mebyube of _CO2, filed December 24, 2008, the text of which in its entirety is included in the text of this specification by reference), chemical processing plants, steel mills, paper mills, cement mills (for example, as described in more detail in provisional application for US patent No. 61/088340, the description of which in its entirety is incorporated into the text of this description by reference), and others industrial enterprises that produce CO ₂ as a by-product. By effluent stream is meant a gas stream (or a similar stream) that is produced as a by-product of an active process in an industrial plant. This gaseous stream can be essentially pure CO2 or a multi-component gaseous stream that includes CO2 and one or more additional gases. Multicomponent gaseous streams (containing CO2) that can be used as a source of CO2 in embodiments of these methods include those found in reduced (for example, synthesis gas, synthesis gas after conversion, natural gas, hydrogen, etc.) and in an oxidized (for example, flue gases from a combustion process, for example, methane combustion) state. If the exhaust gases contain NO _X 8O _X , volatile organic compounds, particles and Nd, then these compounds, together with carbonate, will be part of the precipitated product. Interesting specific multicomponent gaseous streams that can be treated in accordance with the object of the present invention include, but are not limited to, oxygen-containing flue gas from power plants operating on fuel combustion; gaseous product from a turbocharged boiler; coal gasification product gas; gaseous product of coal gasification after conversion; gaseous product of anaerobic enzymatic decomposition reactor; natural gas flow from the wellhead; natural gas after reforming or methane hydrates, etc. If the gas contains both carbon dioxide and gaseous oxygen, the gas can be used both as a source of carbon dioxide and as a source of oxygen. For example, flue gases obtained by burning oxygen and methane may contain gaseous oxygen and can provide a source of both gaseous carbon dioxide and gaseous oxygen.

Thus, effluent streams can be obtained from various types of industrial plants. Suitable effluents for this invention include effluents, for example flue gas obtained from an industrial plant that burns fossil fuels (e.g. coal, oil, natural gas) or man-made fuel products from naturally occurring fossil fuel deposits (e.g. bituminous sands, heavy oils, oil shales, etc.). In some embodiments, an exhaust stream suitable for the devices and methods of this invention comes from a coal-fired power plant, such as a coal dust fired power plant; a coal-fired power plant in supercritical conditions; a massive coal-fired power plant; fluidized bed coal-fired power plants. In some embodiments, the source of the effluent is a gas or oil-fired boiler and steam turbine power plants; power plants with a gas turbine with a simple cycle, in which the boiler runs on gas or oil; or power plants with a gas turbine with a combined cycle, in which the boiler runs on gas or oil. In some embodiments, waste streams are used from power plants that burn synthesis gas (i.e., gas that is obtained by gasification of organic substances, such as coal, biomass, etc.). In some embodiments, waste streams are used from combined cycle plants with on-cycle coal gasification. In some embodiments, waste streams from a steam generator with heat recovery are used to create compositions in accordance with the devices and methods provided herein.

Cement plant effluents are also suitable for the devices and methods provided in the text of this description. Cement plant effluents include effluents from plants operating both wet and dry; and these plants may use shaft furnaces or rotary kilns, and may include decarbonizers. Each of these industrial plants can burn one type of fuel, or it can burn two or more types of fuel, sequentially or simultaneously.

Although carbon dioxide may be present in ordinary atmospheric air, due to its very low concentration, carbon dioxide from atmospheric air cannot provide enough carbon dioxide to achieve the formation of bicarbonate and / or carbonate upon contact of carbon from a carbon source with catholyte. In some embodiments of the device and method, the pressure inside the electrochemical device may be higher than the external atmospheric pressure, and therefore atmospheric carbon dioxide can be prevented from leaking into the catholyte.

The contact device or contactor includes any means for bringing carbon from the carbon source into contact with the catholyte inside the cathode compartment or outside the cathode compartment. Such means for bringing carbon into contact with the catholyte or contactors configured to bring carbon from the carbon source into contact with the cathode compartment are well known in the art and include, but are not limited to, injectors, pipes, channels, conduits and the like. In some 57,024,710 locations, the device includes a channel that directs carbon into the catholyte inside the cathode compartment. It should be understood that if carbon from a carbon source is brought into contact with the catholyte inside the cathode compartment, carbon can be introduced into the catholyte from the bottom of the cell, from the top of the cell, from the side inlet of the cell and / or from all inlets, depending on the amount required carbon in the cathode compartment. The amount of carbon from the carbon source inside the cathode compartment may depend on the flow rate of the solution, the required pH of the catholyte and / or cell size. Such optimization of the amount of carbon supplied from the carbon source is within the scope of this invention. In some embodiments, carbon from a carbon source is selected from carbon dioxide gas from an industrial process or a carbon dioxide solution from a gas-liquid contactor that is in contact with carbon dioxide gas from an industrial process.

In some embodiments, the cathode compartment includes a baffle that helps facilitate the flow of carbon dioxide gas and / or carbon dioxide solution into the cathode compartment. In some embodiments, the baffle can help prevent the mixing of carbon dioxide gas with oxygen gas and / or the mixing of carbon dioxide gas in the cathode compartment with hydrogen gas in the anode compartment. In some embodiments, the septum results in a catholyte containing both a gaseous form of carbon dioxide and a dissolved form of carbon dioxide. In some embodiments, the apparatus provided herein includes a baffle that separates the catholyte into a first part of catholyte and a second part of catholyte, where a second part of catholyte, including dissolved carbon dioxide, is in contact with the cathode, and where a first part of catholyte, including dissolved carbon dioxide and gaseous carbon dioxide, in contact with the second part of the catholyte under the septum. In this device, the partition is located in the catholyte so that the gas, for example carbon dioxide in the first part of the catholyte, is isolated from the catholyte in the second part of the catholyte. Thus, the baffle can serve as a means of preventing the mixing of gases at the cathode and / or gases and / or vapors coming from the anode. Such a partition is described in US publication No. 2010/0084280, registered November 12, 2009, which in its entirety is incorporated into the text of this description by reference.

In some embodiments, the carbon source is a gas-liquid contactor that provides a dissolved form or carbon dioxide solution containing CO2, carbonic acid, bicarbonate ions, carbonate ions, or a combination thereof. In some embodiments, a solution in which partially or completely dissolved CO ₂ is introduced is prepared by sparging or dispersing a stream of gaseous CO2 through a suspension or solution to obtain CO2-containing water. In some embodiments, the suspension or solution in which the CO2 is introduced includes a proton-removing agent obtained from a catholyte of an electrochemical cell, as described herein. In some embodiments, the gas-liquid contactor may include a bubble chamber in which gaseous CO2 is bubbled through a suspension or solution containing a proton-removing agent. In some embodiments, the contactor may comprise a spray tower in which the slurry or solution comprising proton-removal agent is sprayed in a gaseous CO2 or solution is circulated through the CO ₂ gas. In some embodiments, the contactor may include a fixed packing layer to increase the contact surface area between gaseous CO ₂ and a solution containing a proton removing agent. For example, a gas-liquid contactor or absorber may contain a suspension or solution or a fixed bed of a sodium carbonate nozzle. CO ₂ is bubbled through this solution or suspension or a fixed bed of packing, wherein the alkaline medium facilitates the dissolution of CO2 in the solution. After dissolution of CO _{2, the} solution may contain bicarbonate, carbonate, or a combination thereof. In some embodiments, a typical fluid temperature in an absorber or contactor is 3237 ° C. An absorber or contact apparatus for absorbing CO ₂ solution is described in US patent application No. 12/721549, registered March 10, 2010, which in its entirety is incorporated into the text of this description by reference. A solution containing carbonate / bicarbonate particles can be removed from a gas-liquid contactor to produce bicarbonate / carbonate products. In some embodiments, the carbonate / bicarbonate solution can be transferred to a catholyte containing alkali. The alkali can substantially or completely convert bicarbonate to carbonate to form a carbonate solution. The carbonate solution can be recycled back to the gas-liquid contactor, or it can be taken from the cathode compartment and treated with divalent cations to produce bicarbonate / carbonate products.

In some embodiments, the alkali obtained in the catholyte can be sent to a gas-liquid contactor, where gaseous carbon dioxide contacts the alkali. After contact with alkali, gaseous carbon dioxide can lead to the formation of carbonic acid, bicarbonations, carbonate ions, or a combination thereof. The dissolved form of carbon dioxide can then be sent back to the cathode compartment, where alkali can convert bicarbonate to carbonate. The carbonate / bicarbonate mixture can then be used for commercial purposes as prepared, or treated with divalent cations, for example, alkaline earth metal ions, to produce alkaline earth metal carbonates / bicarbonates.

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In some embodiments, the device includes a catholyte circulation system configured to select and circulate catholyte in the device. In some embodiments, the catholyte circulation system includes a gas-liquid contactor located outside the cathode compartment, which is configured to contact carbon from the carbon source with the circulating catholyte and recirculate the electrolyte in the device. Since the pH of the catholyte can be adjusted by taking and / or circulating the catholyte / carbon from the carbon source from the device, the pH of the catholyte containing compartment can be adjusted by adjusting the amount of catholyte removed from the device passing through the gas-liquid contactor and / or recycled back to the cathode compartment .

In some embodiments, the carbon source is a bicarbonate saline solution. Bicarbonate saline is as described in provisional patent application US No. 61/433641, registered January 18, 2011, and provisional patent application US No. 61/408325, registered October 29, 2010, which are fully incorporated to the text of this description by reference. As used herein, the term bicarbonate saline solution includes any saline solution containing bicarbonate ions. In some embodiments, the saline is a synthetic saline, for example, saline containing bicarbonate, for example, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, etc. In some embodiments, the saline solution is a saline solution of natural origin, for example, underground saline, for example, from naturally occurring lakes. In some embodiments, a bicarbonate saline solution is made from subterranean saline solutions, such as, but not limited to, carbonate saline solutions, alkaline saline solutions, solid saline solutions and / or alkaline solid saline solutions. In some embodiments, the bicarbonate saline solution is made from minerals; while the minerals are crushed and dissolved in saline and, possibly, further processed. Minerals can be found below the surface, on the surface or below the surface of lakes. Bicarbonate saline can also be made from evaporite (sedimentary salt). The bicarbonate salt solution may include other carbon oxyanions, in addition to bicarbonate (HCO ₃ ^- ), for example, but not limited to, carbonic acid (H ₂ CO ₃ ) and / or carbonate (CO ₃ ^2- ).

In some embodiments of the electrochemical cells described herein, the device is configured to produce carbonate ions by reacting carbon, for example, CO ₂ , carbonic acid, bicarbonate ions, carbonate ions, or a combination thereof, from a carbon source, with alkali, for example , sodium hydroxide, from catholyte. In some embodiments (not shown in the drawings), carbon from a carbon source, for example, a gaseous form of carbon dioxide, can be brought into contact with the catholyte inside the cathode compartment, and the catholyte containing hydroxide / carbonate / bicarbonate can be removed from the cathode compartment and brought into contact using a gas-liquid contactor outside the cathode compartment. In such embodiments, the catholyte from the gas-liquid contactor can again be brought into contact with the catholyte inside the cathode compartment.

For devices where carbon from a carbon source is in contact with the catholyte outside the cathode compartment, it is possible to select the catholyte containing alkali from the cathode compartment and add it to a container containing carbon from the carbon source. The container may have an inlet for a carbon source, for example, a pipe or conduit, etc., or a conduit in conjunction with a gaseous stream of CO2, a solution containing a dissolved form of CO2, and / or a bicarbonate salt solution. The container may also be in fluid communication with the reactor where it is possible to obtain, modify and / or store a carbon source, such as, for example, bicarbonate saline.

For devices where carbon from a carbon source is brought into contact with the catholyte inside the cathode compartment, the catholyte containing alkali, bicarbonate and / or carbonate can be removed from the cathode compartment and brought into contact with alkaline earth metal ions, as described herein, to produce bicarbonate / carbonate products.

Components of an electrochemical cell.

The methods and devices provided in the text of this description include one or more of the following components.

In some embodiments, the anode may comprise a corrosion resistant electrically conductive substrate. For example, not limited to, amorphous carbon, such as soot; fluorinated carbons, such as the specially fluorinated carbons described in US Pat. No. 4,908,198, marketed under the trade name §PC ™ carbons. Other examples of electrically conductive base materials include, but are not limited to, substoichiometric titanium oxides, such as Magnely phase substoichiometric oxides of titanium, having the formula ΤίΘ _χ , in which x is in the range from about 1.67 to about 1.9. For example, titanium oxide Τί ₄ Ο ₇ . In some embodiments, carbon-based materials provide a mechanical basis for HDE, or are used in admixture with materials to improve electrical conductivity; but they cannot be used as a catalyst support to prevent corrosion.

In some embodiments, gas diffusion electrodes or conventional electrodes described herein comprise an electrocatalyst that promotes electrochemical dissociation, for example, oxygen reduction at the cathode. Examples of electrocatalysts include, but are not limited to, finely divided metals or alloys of platinum group metals such as platinum, palladium, ruthenium, rhodium and iridium (for example, a titanium network coated with a mixed oxide P1-1g; or titanium coated with a plated platinum method); electrocatalytic metal oxides; organometallic macrocyclic compounds, and other electrocatalysts well known in the art for electrochemical oxygen reduction.

In some embodiments, the electrodes described herein relate to porous homogeneous composite structures, as well as to heterogeneous, layered, composite structures in which each layer may have a different physical and compositional structure, for example, porosity and an electrically conductive base, in order to prevent electrode flooding and loss three-phase interface, and the resulting electrode characteristics.

The electrodes provided in the text of this description may include anodes and cathodes having porous polymer layers on or near the surface of the electrode facing the anolyte or catholyte solution, which can help reduce electrode penetration and clogging. Stable polymer resins or films containing resins formed from non-ionic polymers, such as polystyrene, polyvinyl chloride, polysulfone, etc., or ion-type charged polymers such as which are formed from polystyrenesulfonic acid, sulfonated copolymers of styrene and vinylbenzene, carboxylated derivatives of polymers, sulfonated or carboxylated polymers having partially or completely Mostly fluorinated hydrocarbon chains, and aminated polymers such as polyvinylpyridine. On the dry side, films of stable microporous polymers can also be included to slow electrolyte penetration. In some embodiments, gas diffusion cathodes include cathodes known in the art that are coated with a high surface area of noble metals such as gold and / or silver, alloys of noble metals, nickel, and the like.

In some embodiments, the electrolyte, including catholyte or cathode electrolyte and / or anolyte or anode electrolyte, or a third electrolyte located between AOM and KOM, in the devices and methods provided herein, includes, but is not limited to, salt or fresh water. Salt water includes, but is not limited to, seawater, brine, and / or hard water. In some embodiments, the catholyte in the devices and methods provided in the text of this description includes, but is not limited to, sea water, fresh water, brine, hard water, hydroxide, for example sodium hydroxide, or a combination thereof. The term salt water is used in its usual sense and refers to a number of different types of aqueous fluids other than fresh water, and the term salt water includes, but is not limited to, hard water, sea water and brine (including underground saline solutions of natural origin or anthropogenic underground saline solutions and human-made saline solutions, for example, wastewater from enterprises operating on geothermal waters, wastewater from desalination plants, etc.), as well as other saline solutions having a miner Alizization is higher than that of fresh water. The brine is water saturated with salt or close to saturation in salt, and having a salinity of 50 parts per thousand or more. Hard water is water that is more saline than fresh water, but not as salty as sea water, and has a salinity in the range of 0.5 to 35 parts per thousand. Sea water is water from the sea or ocean and has a salinity of 35 to 50 parts per thousand. The source of salt water can be a source existing in nature, for example, the sea, ocean, lake, swamp, estuary, lagoon, etc., or a source created by man. In some embodiments, the devices provided herein include salt water from ground saline solutions. In some embodiments, salt is added to depleted salt water taken from electrochemical cells and recycled back to the electrochemical cell.

In some embodiments, the electrolyte, including catholyte, and / or anolyte, and / or a third electrolyte, such as salt water, includes water containing more than 1% chloride, for example NaCl, or more than 10% NaCl, or more than 20% NaCl, or more than 30 % NaCl, or more than 40% NaCl, or more than 50% NaCl, or more than 60% NaCl, or more than 70% NaCl, or more than 80% NaCl, or more than 90% NaCl, or from 1 to 99% NaCl, or from 1 up to 95% NaCl, or from 1 to 90% NaCl, or from 1 to 80% NaCl, or from 1 to 70% NaCl, or from 1 to 60% NaCl, or from 1 to 50% NaCl, or from 1 to 40 % NaCl, or from 1 to 30% NaCl, or from 1 to 20% NaCl, or from 1 to 10% NaCl, or from 10 to 99% NaCl, or from 10 to 95% NaCl, or from 10 to 90% NaCl, or from 10 to 80% NaCl, or from 10 to 70% NaCl, or from 10 to 60% NaCl, or from 10 to 50% NaCl, or from 10 to 40% NaCl, or from 10 to 30% NaCl, or from 10 to 20% NaCl, or from 20 to 99% NaCl, or from 20 to 95% NaCl, or from 20 to 90% NaCl, or from 20 to 80% NaCl, or 20 to 70% NaCl, or from 20 to 60% NaCl, or from 20 to 50% NaCl, or from 20 to 40% NaCl, or from 20 to 30% NaCl, or from 30 to 99% NaCl, or from 30 to 95% NaCl, or 30 to 90% NaCl, or 30 to 80% NaCl, or 30 to 70% NaCl, or 30 to 60% NaCl, or 30 to 50% NaCl, or 30 to 40% NaCl, or from 40 to 99% NaCl, or from 40 to 95% NaCl, or from 40 to 90% NaCl, or from 40 to 80% NaCl, or from 40 to 70% NaCl, or from 40 to 60% NaCl, or from 40 to 50% NaCl, or from 50 to 99% NaCl, or from 50 to 95% NaCl, or from 50 to 90% NaCl, or from 50 to 80% NaCl, or 50 to 70% NaCl, or from 50 to 60% NaCl, or from 60 to 99% NaCl, or from 60 to 95% NaCl, or from 60 to 90% NaCl, or from 60 to

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80% No. C1, or from 60 to 70% No. C1, or from 70 to 99% No. C1, or from 70 to 95% No. C1, or from 70 to 90% No. C1, or from 70 to 80% No. C1, or from 80 to 99% No. C1, or from 80 to 95% No. C1, or from 80 to 90% No. C1, or from 90 to 99% No. C1, or from 90 to 95% No. C1. In some embodiments, the aforementioned percentage composition is applied to ammonium chloride, iron chloride, sodium bromide, sodium iodide or sodium sulfate as an electrolyte. The percentages given here include wt.%, Or% wt./wt., Or% wt./about. It should be understood that in all electrochemical devices described herein that contain sodium chloride, the electrolyte can be replaced with other suitable electrolytes, for example, but not limited to, ammonium chloride, sodium bromide, sodium iodide, sodium sulfate, or a combination thereof.

In some embodiments, the catholyte, for example, salt water, fresh water and / or sodium hydroxide, does not include alkaline earth metal ions or divalent cations. Used in the text of this description, the term divalent cations includes alkaline earth metal ions, for example, but not limited to, calcium, magnesium, barium, strontium, radium, etc. In some embodiments, a catholyte, for example, salt water, fresh water and / or sodium hydroxide, comprises less than 1% by weight of divalent cations. In some embodiments, a catholyte, for example seawater, fresh water, brine, hard water and / or sodium hydroxide, comprises less than 1 wt.% Of divalent cations. In some embodiments, the catholyte, for example seawater, fresh water, brine, hard water and / or sodium hydroxide, contains bicalent cations, including, but not limited to, calcium, magnesium, and a combination thereof. In some embodiments, a catholyte, for example seawater, fresh water, brine, hard water and / or sodium hydroxide, contains less than 1 wt.%, Divalent cations, including, but not limited to, calcium, magnesium, and a combination thereof.

In some embodiments, the catholyte, for example seawater, fresh water, brine, hard water and / or sodium hydroxide, contains less than 1% w / w, or less than 5% w / w, or less than 10% w / w ., or less than 15% w / w, or less than 20% w / w, or less than 25% w / w, or less than 30% w / w, or less than 40% w / w ., or less than 50% w / w, or less than 60% w / w, or less than 70% w / w, or less than 80% w / w, or less than 90% w / w ., or less than 95% wt./wt., or from 0.05 to 1% wt./wt., or from 0.5 to 1% wt./wt., or from 0.5 to 5% wt. / wt., or from 0.5 to 10% wt./wt., or from 0.5 to 20% wt./wt., or from 0.5 to 30% ma C. / wt., or from 0.5 to 40% wt./wt., or from 0.5 to 50% wt./wt., or from 0.5 to 60% wt./wt., or from 0.5 to 70% w / w, or 0.5 to 80% w / w, or 0.5 to 90% w / w, or 5 to 8% w / w ., or from 5 to 10% wt./wt., or from 5 to 20% wt./wt., or from 5 to 30% wt./wt., or from 5 to 40% wt./wt., or from 5 to 50% w / w, or from 5 to 60% w / w, or from 5 to 70% w / w, or from 5 to 80% w / w, or 5 to 90% w / w, or 10 to 20% w / w, or 10 to 30% w / w, or 10 to 40% w / w, or 10 to 50% w / w, or 10 to 60% w / w, or 10 to 70% w / w, or 10 to 80% w / w, or 10 to 90% wt./wt., or t 30 to 40% wt./wt., or from 30 to 50% wt./wt., or from 30 to 60% wt./wt., or from 30 to 70% wt./wt., or from 30 up to 80% w / w, or from 30 to 90% w / w, or from 50 to 60% w / w, or from 50 to 70% w / w, or from 50 to 80 % w / w, or from 50 to 90% w / w, or from 75 to 80% w / w, or from 75 to 90% w / w, or from 80 to 90% w ./mass., or from 90 to 95% wt./wt. divalent cations, including, but not limited to, calcium, magnesium, and a combination thereof.

In some embodiments, the catholyte includes, but is not limited to, sodium hydroxide, sodium bicarbonate, sodium carbonate, or a combination thereof. In some embodiments, the catholyte includes, but is not limited to, sodium or potassium hydroxide. In some embodiments, the catholyte includes, but is not limited to, sodium hydroxide, divalent cations, or a combination thereof. In some embodiments, the catholyte includes, but is not limited to, sodium hydroxide, sodium bicarbonate, sodium carbonate, divalent cations, or a combination thereof. In some embodiments, the catholyte includes, but is not limited to, sodium hydroxide, calcium bicarbonate, calcium carbonate, magnesium bicarbonate, magnesium carbonate, calcium-magnesium carbonate, or a combination thereof. In some embodiments, the catholyte includes, but is not limited to, salt water, sodium hydroxide, bicarbonate saline, or a combination thereof. In some embodiments, the catholyte includes, but is not limited to, salt water and sodium hydroxide. In some embodiments, the catholyte includes, but is not limited to, fresh water and sodium hydroxide. In some embodiments, the catholyte comprises fresh water free of alkalinity or divalent cations. In some embodiments, the catholyte includes, but is not limited to, fresh water, sodium hydroxide, sodium bicarbonate, sodium carbonate, divalent cations, or a combination thereof.

In some embodiments, the anolyte includes, but is not limited to, fresh water and metal ions. In some embodiments, the anolyte includes, but is not limited to, salt water and metal ions. In some embodiments, the anolyte comprises a metal ion solution.

In some embodiments, depleted salt water from the cell can be recycled back to the cell. In some embodiments, the catholyte comprises 1-90%, 1-50%, or 1-40, or 1-30%, or 1-15%, or 1-20%, or 1-10%, or 5-90%, or 5-50%, or 5-40%, or 5-30%, or 5-20%, or 5-10%, or 10-90%, or 10-50%, or 10-40%, or 10- 30%, or 10-20%, or 15-20%, or 15-30%, or 20-30% sodium hydroxide solution. In some embodiments, the anolyte comprises 0-5 M, or 0-4.5 M, or 0-4 M, or 0-3.5 M, or 0-3 M, or 0-2.5 M, or 0-2 M, or 0-1.5 M, or 0-1 M, or 1-5 M, or 1-4.5 M, or 1-4 M, or 1-3.5 M, or

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1-3 M, or 1-2.5 M, or 1-2 M, or 1-1.5 M, or 2-5 M, or 2-4.5 M, or 2-4 M, or 2- 3.5 M, or 2-3 M, or 2-2.5 M, or 3-5 M, or 3-4.5 M, or 3-4 M, or 3-3.5 M, or 4- 5 M, or 4.5-5 M metal ion solution. In some embodiments, gaseous oxygen is not formed at the anode. In some embodiments, chlorine gas is not formed at the anode.

In some embodiments, the catholyte and anolyte are separated, partially or completely, by an ion exchange membrane. In some embodiments, the ion exchange membrane is an anion exchange membrane or a cation exchange membrane. In some embodiments, cation exchange membranes in an electrochemical cell, as described herein, are conventional and can be obtained, for example, from LKAY Ka8s1 (Tokuo, 1aran); or at Mtbgans ΙηΙοΓηαΙίοηαΙ о £ С1сп Кейк, N1; or ΌϋΡοηΐ (USA). Examples of COM include, but are not limited to, Ν2030 \ νΧ Latitude). P8020 / P8080 (Eastuf and P6801 (Ac1p1cx). COM, which are desirable in the methods and devices of this invention, have minimal ohmic losses, more than 90% selectivity and high stability in concentrated alkali. AOM in the methods and devices of this invention are the effects of anolytes - concentrated solutions of metal salts - and streams of saturated saline solution.It is desirable that the AOM allow the salt ion, for example, chloride ion, to pass into the anolyte, but prevent the metal ions from leaving the anoly In some embodiments, metal salts can form various ionic particles (cationic, anionic and / or neutral), including, but not limited to, MC1 +, MC1 ₂ ^- , MC1 ₂ ⁰ , M ² +, etc., and preferably so that such complexes do not pass through the AOM and clog membranes. In the examples, several membranes are provided that have been tested for the methods and devices of this invention and which have been found to interfere with the passage of metals.

Accordingly, methods provided in the text of this description include contacting the anode with a metal ion in the anolyte in the anode compartment; transfer of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; the formation of alkali, water or hydrogen gas at the cathode; and preventing the migration of metal ions from the anolyte to the catholyte by using an anion-exchange membrane; wherein the anion exchange membrane has an ohmic resistance of less than 3 ohm-cm ² , or less than 2 ohm-cm ² , or less than 1 ohm-cm ² . In some embodiments, the anion exchange membrane has an ohmic resistance of 1 to 3 ohm-cm ² . In some embodiments, methods are provided comprising contacting the anode with a metal ion in the anolyte in the anode compartment; transfer of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; the formation of alkali, water or hydrogen gas at the cathode; and preventing the migration of metal ions from the anolyte to the catholyte by using an anion-exchange membrane; however, the anion exchange membrane retains more than 80%, or more than 90%, or more than 99%, or approximately 99.9% of all metal ions from the anolyte.

Also provided are devices comprising an anode in contact with a metal ion in the anolyte in the anode compartment, wherein the anode is configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; the cathode is in contact with the catholyte in the cathode compartment, while the cathode is configured to form alkali, water or hydrogen gas in the cathode compartment; and an anion exchange membrane, wherein the anion exchange membrane has an ohmic resistance of less than 3 ohm-cm ² , or less than 2 ohm-cm ² ; or less than 1 ohm-cm ² . In some embodiments, the anion exchange membrane has an ohmic resistance of 1 to 3 ohm-cm ² . In some embodiments, devices are provided, including bringing the anode into contact with a metal ion in the anolyte in the anode compartment, wherein the anode is configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; the cathode is in contact with the catholyte in the cathode compartment, while the cathode is configured to form alkali, water or hydrogen gas in the cathode compartment; and an anion exchange membrane, wherein the anion exchange membrane traps more than 80%, or more than 90%, or more than 99%, or about 99.9% of metal ions from the anolyte.

Also provided in the text of this description are methods comprising contacting the anode with a metal ion in the anolyte in the anode compartment; transfer of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; alkali formation at the cathode; separating the anolyte from the compartment containing the saline solution with an anion exchange membrane; separating the catholyte from the compartment containing the saline solution by a cation exchange membrane; and preventing the migration of metal ions from the anolyte into the compartment containing the saline solution by using an anion exchange membrane that has an ohmic resistance of less than 3 Ohm-cm ² ; or less than 2 ohm-cm ² ; or less than 1 ohm-cm ² . In some embodiments, the anion exchange membrane has an ohmic resistance of 1 to 3 ohm-cm ² . In some embodiments, methods are provided comprising contacting the anode with a metal ion in the anolyte in the anode compartment; transfer of a metal ion at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte in the cathode compartment; getting alkali at the cathode; separating the anolyte from the compartment containing the saline solution with an anion exchange membrane; separation of catholyte from the compartment containing 62 024710 saline solution with a cation exchange membrane; and preventing the migration of metal ions from the anolyte to the compartment containing the saline solution by using an anion exchange membrane that traps more than 80%, or more than 90%, or more than 99%, or about 99.9% of all metal ions from the anolyte.

Also provided are devices comprising an anode in contact with a metal ion in the anolyte in the anode compartment, wherein the anode is configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; the cathode is in contact with the catholyte in the cathode compartment, while the cathode is configured to produce alkali in the cathode compartment; an anion exchange membrane separating the anolyte from the compartment in which the saline solution is located; and a cation exchange membrane separating the catholyte from the compartment in which the saline solution is located; wherein the anion exchange membrane has an ohmic resistance of less than 3 ohm-cm ² , or less than 2 ohm-cm ² ; or less than 1 ohm-cm ² . In some embodiments, the anion exchange membrane has an ohmic resistance of 1 to 3 ohm-cm ² . In some embodiments, devices are provided, including bringing the anode into contact with a metal ion in the anolyte in the anode compartment, wherein the anode is configured to transfer the metal ion in the anode compartment from a lower oxidation state to a higher oxidation state; the cathode is in contact with the catholyte in the cathode compartment, while the cathode is configured to form alkali in the cathode compartment; an anion exchange membrane separating the anolyte from the compartment in which the saline solution is located; and a cation exchange membrane separating the catholyte from the compartment in which the saline solution is located; however, the anion exchange membrane retains more than 80%, or more than 90%, or more than 99%, or approximately 99.9% of all metal ions from the anolyte.

The methods and devices described above, including AOM, further include treating the anolyte containing the metal ion with a higher oxidation state with hydrogen gas, an unsaturated hydrocarbon, or a saturated hydrocarbon, as described herein.

Examples of cation exchange membranes include, but are not limited to, a cationic membrane consisting of a perfluorinated polymer containing anionic groups, for example, sulfonic groups and / or carboxyl groups. However, it can be understood that in some embodiments, depending on the need to restrict or allow the migration of specific cationic or anionic particles between electrolytes, a cation exchange membrane with higher restrictive properties can be used, which, therefore, allows only one type of cation to migrate, at the same time time restricting the migration of other types of cations, such as, for example, a cation-exchange membrane, which allows the migration of sodium ions into the catholyte from the anolyte, while limiting the migration other ions from anolyte to catholyte. Similarly, in some embodiments, depending on the need to restrict or allow the migration of specific types of anions between electrolytes, an anion exchange membrane can be used that has higher restrictive properties and, thus, allows the migration of some types of anions, while limiting the migration of others types of anions, such as, for example, an anion-exchange membrane, which allows chloridions to migrate to the anolyte from catholyte, while limiting the migration of hydroxide ions from catholy that in the anolyte. Such limiting cation exchange and anion exchange membranes are commercially available and one skilled in the art can select them.

In some embodiments, a device is provided comprising one or more anion exchange membranes and cation exchange membranes located between the anode and cathode. In some embodiments, membranes should be selected so that they can optionally work in an acidic and / or alkaline electrolyte solution. Other desirable membrane characteristics include high ion selectivity, low ionic resistance, high bursting strength, and high stability in an acidic electrolyte solution in a temperature range of 0 to 100 ° C. or higher, or in an alkaline solution in the same temperature range. In some embodiments, it is desirable that the ion exchange membrane prevent the transfer of the metal ion from the anolyte to the catholyte. In some embodiments, a membrane that is stable in the range from 0 to 90 ° C, or from 0 to 80 ° C, or from 0 to 70 ° C, or from 0 to 60 ° C, or from 0 to 50 ° C can be used. or from 0 to 40 ° C, or from 0 to 30 ° C, or from 0 to 20 ° C, or from 0 to 10 ° C, or higher. In some embodiments, you can use a membrane that is stable in the range of 0 to 90 ° C, or from 0 to 80 ° C, or from 0 to 70 ° C, or from 0 to 60 ° C, or from 0 to 50 ° C. or from 0 to 40 ° C, but unstable at higher temperatures. For other embodiments, it may be useful to use specific ion-specific ion-exchange membranes that allow the migration of one type of cation, but not the other; or the migration of one type of anion, but not the other, to obtain the desired product or products in the electrolyte. In some embodiments, the membrane can be stable and operable in the device, for the required length of time, for example, for several days, weeks or months or years, at temperatures in the range from 0 to 90 ° C, or from 0 to 80 ° C. or from 0 to 70 ° C, or from 0 to 60 ° C, or from 0 to 50 ° C, or from 0 to 40 ° C, or from 0 to 30 ° C, or from 0 to 20 ° C, or from 0 to 10 ° C and above and / or below. In some embodiments, for example, the membranes can be stable and functional for at least 1 day, at least 5 days, 10 days, 15 days, 20 days, 100 days,

- 63,024,710

1000 days, 5-10 years or more, at electrolyte temperatures of 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5 ° C or more or less.

The ohmic resistance of the membranes can affect the voltage drop across the anode and cathode, for example, as the ohmic resistance of the membranes increases, the voltage at the anode and cathode can increase, and vice versa. Membranes that can be used include, but are not limited to, membranes with relatively low ohmic resistance and relatively high ion mobility; and membranes with relatively high hydration characteristics that increase with temperature, thereby reducing ohmic resistance. By choosing membranes with lower ohmic resistance known in the art, it is possible to reduce the voltage drop across the anode and cathode at a particular temperature.

Ion channels including acidic groups can be distributed across the membranes. These ion channels can go from the inner surface of the matrix to the outer surface, and acid groups can effectively bind water in a reversible reaction in the form of hydration water. This binding of water in the form of hydration water can occur in accordance with the kinetics of the first order reaction, so that the reaction rate is proportional to temperature. Therefore, membranes can be selected so as to provide a relatively low ohmic and ionic resistance, while at the same time providing increased strength and resistance in the system in the range of operating temperatures.

In some embodiments, carbon from a carbon source, when brought into contact with the catholyte inside the cathode compartment, reacts with hydroxide ions and produces water and carbonate ions, depending on the pH of the catholyte. Adding carbon from a carbon source to catholyte can lower the catholyte's pH. Thus, depending on the degree of alkalinity required in the catholyte, the pH of the catholyte can be adjusted and, in some embodiments, maintained in the range from 6 to 12, from 7 to 14 or higher, or from 7 to 13, or from 7 to 12, or from 7 to 11, or from 7 to 10, or from 7 to 9, or from 7 to 8, or from 8 to 14 or higher, or from 8 to 13, or from 8 to 12, or from 8 to 11, or from 8 to 10, or from 8 to 9, or from 9 to 14 or higher, or from 9 to 13, or from 9 to 12, or from 9 to 11, or from 9 to 10, or from 10 to 14 or higher, or from 10 to 13, or from 10 to 12, or from 10 to 11, or from 11 to 14 or higher, or from 11 to 13, or from 11 to 12, or from 12 to 14 or higher, and whether from 12 to 13, or from 13 to 14 or higher. In some embodiments, the pH of the catholyte can be adjusted to any value of 7 to 14 or higher; or less than 12; or 7.0; 7.5; 8.0; 8.5; 9.0; 9.5; 10.0; 10.5; 11.0; 11.5; 12.0; 12.5; 13.0; 13.5; 14.0 and / or higher.

Similarly, in some embodiments of the device, the pH of the anolyte is adjusted and maintained in the range of 0 to 7; or from 0 to 6; or from 0 to 5; or from 0 to 4; or from 0 to 3; or from 0 to 2; or from 0 to 1. Since the voltage at the anode and cathode can depend on several factors, including the pH difference between the anolyte and catholyte (as can be determined by the well-known Nernst equation), in some embodiments, the pH of the anolyte can be adjusted to a value from 0 to 7 , including 0; 0.5; 1.0; 1.5; 2.0; 2.5; 3.0; 3.5; 4.0; 4,5; 5.0; 5.5; 6.0; 6.5; and 7, depending on the required operating voltage at the anode and cathode. Thus, in equivalent systems, if it is desirable to reduce the used energy and / or voltage at the anode and cathode, for example, as in the chlor-alkali process, then to achieve the desired pH difference between the anolyte and catholyte, carbon from the carbon source can be added to the catholyte, as described in this text.

The device can be configured to create any desired pH difference between the anolyte and catholyte by changing the anolyte pH, catholyte pH, catholyte hydroxide concentration, anolyte selection and replenishment, catholyte selection and replenishment and / or the amount of carbon from the carbon source added to the catholyte. By varying the pH difference between the anolyte and the catholyte, the voltage at the anode and at the cathode can be controlled. In some embodiments, the device is configured to produce a pH difference between the anolyte and catholyte of at least 4 pH units, at least 5 pH units, at least 6 pH units, at least 7 pH units, at least 8 pH units at least 9 pH units, at least 10 pH units, at least 11 pH units, at least 12 pH units, at least 13 pH units, at least 14 pH units, or 4 to 12 pH units , or from 4 to 11 pH units, or from 4 to 10 pH units, or from 4 to 9 pH units, or from 4 to 8 pH units, or 4 to 7 pH units, or from 4 to 6 pH units, or from 4 to 5 pH units, or from 3 to 12 pH units, or from 3 to 11 pH units, or from 3 to 10 pH units, or from 3 to 9 pH units, or from 3 to 8 pH units, or from 3 to 7 pH units, or from 3 to 6 pH units, or from 3 to 5 pH units, or from 3 to 4 pH units, or from 5 to 12 units pH, or from 5 to 11 pH units, or from 5 to pH units, or from 5 to 9 pH units, or from 5 to 8 pH units, or from 5 to 7 pH units, or from 5 to 6 pH units, or from 6 to 12 pH units, or from 6 to 11 pH units, or from 6 to 10 pH units, or from 6 to 9 pH units, or from 6 to 8 pH units, or from 6 to 7 pH units, silt and from 7 to 12 pH units, or from 7 to 11 pH units, or from 7 to 10 pH units, or from 7 to 9 pH units, or from 7 to 8 pH units, or from 8 to 12 pH units, or 8 to 11 pH units, or from 8 to 10 pH units, or from 8 to 9 pH units, or from 9 to 12 pH units, or from 9 to 11 pH units, or from 9 to 10 pH units, or from 10 to 12 pH units, or 10 to pH units, or 11 to 12 pH units. In some embodiments, the device is configured to produce a pH difference between anolyte and catholyte of at least 4 units

- 64,024,710 pH.

In some embodiments in the methods and devices provided in the text of this description, the anolyte and catholyte in the electrochemical cell operate at room temperature or at elevated temperatures, for example, at temperatures above 40 ° C, or above 50 ° C, or above 60 ° C, or above 70 ° C, or above 80 ° C, or from 30 to 70 ° C.

Obtaining bicarbonate and / or carbonate products.

In some embodiments, the methods and devices provided herein are adapted to treat a carbonate / bicarbonate solution obtained after the catholyte is contacted with carbon from a carbon source. In some embodiments, a solution containing carbonate and / or bicarbonate is treated with divalent cations, for example, but not limited to calcium and / or magnesium, to produce calcium and / or magnesium carbonate and / or bicarbonate. An exemplary embodiment of such processes is shown in FIG. thirteen.

As illustrated in FIG. 13, process 1300 illustrates methods and apparatus for treating a carbonate / bicarbonate solution obtained after the catholyte is contacted with carbon from a carbon source. In some embodiments, the solution is precipitated in precipitant 1301. In some embodiments, the solution includes sodium hydroxide, sodium carbonate and / or sodium bicarbonate. In some embodiments, the device is configured to treat bicarbonate and / or carbonate ions in a catholyte with an alkaline earth metal ion or divalent cation, including, but not limited to, calcium, magnesium, and a combination thereof. The term divalent cation, as used throughout this specification, includes any solid or solution that contains a divalent cation, for example, alkaline earth metal ions, or any aqueous medium containing alkaline earth metals. Alkaline earth metals include calcium, magnesium, strontium, barium, etc., or combinations thereof. Divalent cations (e.g., cations of alkaline earth metals such as Ca ² + and Mg ² ') can be found in industrial wastes, seawater, brines, hard water minerals and many other suitable sources. Water containing alkaline earth metals includes fresh water or salt water, depending on how the water is used. In some embodiments, the water used in this process includes one or more alkaline earth metals, for example, magnesium, calcium, etc. In some embodiments, alkaline earth metal ions are present in an amount of from 1 to 99 wt.%, Or from 1 to 95 wt.%, Or from 1 to 90 wt.%, Or from 1 to 80 wt.%, Or from 1 to 70 wt.%, Or from 1 to 60 wt.%, Or from 1 to 50 wt.%, Or from 1 to 40 wt.%, Or from 1 to 30 wt.%, Or from 1 to 20 wt.%, or from 1 to 10 wt.%, or from 20 to 95 wt.%, or from 20 to 80 wt.%, or from 20 to 50 wt.%, or from 50 to 95 wt.%, or from 50 to 80 wt.%, or from 50 to 75 wt.%, or from 75 to 90 wt.%, or from 75 to 80 wt.%, or from 80 to 90 wt.%, from a solution containing alkaline earth metal ions. In some embodiments, alkaline earth metal ions are present in salt water, for example, sea water. In some embodiments, the source of divalent cations is hard water or hard brines of natural origin. In some embodiments, calcium-enriched waters may be combined with minerals including magnesium silicate, such as olivine or serpentine.

In some embodiments, the source of divalent cations, for example, but not limited to calcium ions, is gypsum (e.g., from the Solve process). After precipitation of calcium carbonate / bicarbonate using a carbonate / bicarbonate solution from the cathode compartment and calcium from gypsum, the mother liquor containing sodium sulfate can be sent to the electrochemical devices described herein. The sodium sulfate solution can be used in combination with metal sulfate, for example, copper sulfate, so that Cu (1) ions are oxidized in the anode compartment to Cu ions (11), and then they are used for sulfonation of hydrogen gas or for sulfonation of unsaturated or saturated hydrocarbons . In such embodiments, the electrochemical system is fully integrated with the deposition process. Such use of gypsum as a source of calcium is described in provisional patent application US No. 61/514879, registered August 3, 2011, which in its entirety is incorporated into the text of this description by reference.

In some places, convenient sources of cations provide industrial effluents from various industrial processes (as well as, in some cases, other materials suitable in this process, for example, metal hydroxide). Such effluents include, but are not limited to, mining waste; fossil fuel ash (e.g. fly ash, fly ash, furnace slag); slag (e.g. iron slag, phosphorus slag); cement kiln waste (e.g. cement dust); refinery / petrochemical industry wastes (e.g., brines from oil and methane fields); coal bed wastes (for example, brines used in the production of gas and coal); paper production waste; saline solution obtained as waste by softening water (for example, effluents from an ion exchange column); silicon processing waste; agricultural wastewater; metal processing waste; effluents from high pH textile mills; and alkaline sludge. In some embodiments, the aqueous solution of cations includes calcium and / or magnesium in amounts ranging from 10 to 50,000 ppm, or from 10 to 10,000 ppm, or from 10 to 5,000 ppm, or from 10 to 1000 ppm, or from 10 to 100 ppm, or from

- 65,024,710 to 50,000 ppm, or from 50 to 10,000 ppm, or from 50 to 1,000 ppm, or from 50 to 100 ppm, or from 100 to 50,000 ppm, or from 100 to 10,000 ppm, or from 100 to 1,000 ppm, or from 100 to 500 ppm, or from 1,000 to 50,000 ppm, or from 1,000 to 10,000 ppm, or from 5,000 to 50,000 ppm, or from 5,000 to 10,000 ppm, or from 10,000 to 50,000 ppm.

A convenient source of cations (e.g., cations of alkaline earth metals such as Ca ² + and Mg ² ') can be fresh water. You can use any number of suitable sources of fresh water, including fresh water sources ranging from sources relatively free of minerals to sources relatively enriched in minerals. Mineral-enriched sources of fresh water can exist in nature, including any of a large number of sources of hard water, lakes or inland seas. Some mineral-rich sources of fresh water, such as alkaline lakes or inland seas (for example, Lake Van in Turkey) also provide a source of pH modifying agent. Mineral-enriched fresh water sources can also be man-made. For example, mineral-depleted (soft) water can be brought into contact with a source of cations, such as alkaline earth metal cations (e.g., Ca ² ′, Md ² ′, etc.), to produce mineral-rich water that is suitable for the methods and devices described herein. Cations or their precursors (e.g., salts, minerals) can be added to fresh water (or any type of water described herein) using any conventional method (e.g., adding solids, suspensions or solutions). In some embodiments, divalent cations selected from Ca ² ′ and MD ² ′ are added to fresh water. In some embodiments, fresh water containing Ca ^{2 ′} is combined with magnesium silicates (eg, olivine or serpentine), or products or forms of processing thereof, to form a solution containing calcium and magnesium cations.

The precipitate obtained after bringing the carbon from the carbon source into contact with the catholyte and divalent cations includes, but is not limited to, calcium carbonate, magnesium carbonate, calcium bicarbonate, magnesium bicarbonate, calcium-magnesium carbonate, or a combination thereof. In some embodiments, the precipitate can be subjected to one or more steps, including, but not limited to, mixing, stirring, exposure to temperature and pH, precipitation, holding time during precipitation, dewatering the precipitate, washing the precipitate with water, ion ratio, concentration of additives, drying, grinding, grinding, storing, aging and curing to obtain a carbonate composition according to this invention. In some embodiments, the deposition conditions are such that the carbonate products are metastable forms, such as, but not limited to, laterite, aragonite, amorphous calcium carbonate, or a combination thereof.

The precipitator 1301 may be a container or a series of containers. The contacting method includes, but is not limited to, direct contacting methods, for example, the passage of a specific volume of water containing cations, for example, alkaline earth metal ions, through a specific volume of catholyte containing sodium hydroxide; means for making contact in direct flow, for example, contact between flows of liquid phases flowing in one direction; and means for making contact in countercurrent, for example, contact between flows of liquid phases flowing in opposite directions; etc. Thus, contact can be achieved through the use of injection devices, bubblers, venturi reactors for fluids, atomizers, gas filters, reactors in the form of spray columns, plates or fixed bed nozzles, etc., as will be convenient. In some embodiments, the contact is carried out by spraying. In some embodiments, contact is made using a packed column. In some embodiments, carbon from a carbon source is added to a source of cations and a catholyte containing hydroxide. In some embodiments, a cationic source and an alkali-containing catholyte are added to carbon from a carbon source. In some embodiments, to carry out the deposition, both the source of cations and carbon from the carbon source are simultaneously added to the catholyte containing alkali in the precipitator.

In some embodiments, in which carbon from a carbon source has been added to the catholyte inside the cathode compartment, the selected catholyte containing hydroxide, bicarbonate and / or carbonate is sent to the precipitant for further reaction with divalent cations. In some embodiments in which carbon from a carbon source and divalent cations have been added to the catholyte inside the cathode compartment, selected catholyte containing sodium hydroxide, calcium carbonate, magnesium carbonate, calcium bicarbonate, magnesium bicarbonate, calcium magnesium carbonate, or a combination thereof, is sent to precipitant for further processing.

Precipitator 1301, containing a solution of calcium carbonate, magnesium carbonate, calcium bicarbonate, magnesium bicarbonate, calcium-magnesium carbonate, or a combination thereof, is subjected to deposition conditions. In the precipitation step, carbonate compounds are precipitated, which may be amorphous or crystalline. These carbonate compounds can form a reaction product comprising carbonic acid, bicarbonate, carbonate, or a mixture thereof. The carbonate precipitate can be a cementitious compound, and it can be either stored in the mother liquor or further processed to obtain cementitious products. Alternatively, the sludge can be further processed to produce hydraulic cement or additional compositions from cementitious materials 66,024,710. Cementitious compositions, hydraulic cements, and additional cementitious compositions are described in US Patent Application No. 12/857248, filed Aug. 16, 2010, which is hereby incorporated by reference in its entirety.

One or more conditions, or one or more precipitation conditions in question, include conditions that alter the physical environment of the water to obtain the desired precipitation product. Such one or more precipitation conditions include, but is not limited to, one or more of the following conditions: temperature, pH, precipitation, dehydration or separation of the precipitate, drying, grinding and storage. For example, the temperature of the water may be within a range suitable for precipitation of the desired composition. For example, the temperature of the water can be increased to a value suitable for precipitation of the desired carbonate compound (s). In such embodiments, the water temperature may be from 5 to 70 ° C., for example from 20 to 50 ° C., including a range from 25 to 45 ° C. While this set of deposition conditions can have a temperature range from 0 to 100 ° C, in some embodiments, the temperature can be raised to obtain the desired precipitation product. In some embodiments, the temperature is raised using energy obtained from sources with low or zero carbon dioxide emissions, for example, solar energy sources, windmills, hydroelectric energy sources, etc.

The residence time of the precipitate in the precipitant until the precipitate is removed from the solution may vary. In some embodiments, the residence time of the precipitate in the solution is more than 5 s, or from 5 s to 1 h, or from 5 s to 1 min, or from 5 to 20 s, or from 5 to 30 s or from 5 to 40 s. Not limited to any theory, it is believed that the residence time of the precipitate may affect particle size. For example, a shorter residence time can give a smaller particle size or more dispersed particles, while a longer residence time can give agglomerated particles or larger particles. In some embodiments, the residence time in the method of this invention can be used to obtain small particles as well as large particles in one or more batches that can be separated, or can be left mixed for the subsequent steps of the method.

The nature of the precipitate can also be influenced by the choice of an appropriate ratio of basic ions. The ratio of basic ions can influence the formation of a polymorphic product, so that the carbonate products are metastable forms, for example, but not limited to, laterite, aragonite, amorphous calcium carbonate, or a combination thereof. In some embodiments, carbonate products may also include calcite. Such polymorphic precipitates are described in US patent application No. 12/857248, registered August 16, 2010, which in its entirety is incorporated into the text of this description by reference. For example, magnesium can stabilize vaterite and / or amorphous calcium carbonate in the precipitate. The deposition rate can also affect the formation of the polymorphic phase of the compound, and it can be controlled in a manner sufficient to obtain the desired precipitation product. The most rapid precipitation can be achieved by introducing the desired polymorphic phase into the solution of nuclei. Without the introduction of nuclei, rapid precipitation can be achieved by rapidly increasing the pH of seawater. The higher the pH, the faster the precipitation can be.

In some embodiments, the set of conditions for obtaining the desired precipitated product from the aqueous phase includes, but is not limited to, water temperature and pH, and in some cases, the concentration of additives and ionic particles in the water. Precipitation conditions may also include factors such as mixing speed, types of disturbances, such as ultrasound, and the presence of seed crystals, catalysts, membranes, or substrates. In some embodiments, precipitation conditions include supersaturation conditions, temperature, pH and / or concentration gradients, or cycling, or a change in any of these parameters. The methods used to obtain the precipitation of carbonate compounds according to this invention can be periodic or continuous. It can be understood that the deposition conditions for obtaining this precipitate in a continuous flow system may differ from the conditions in a batch system.

After the carbonate precipitate is obtained from water, the precipitated carbonate composition obtained can be separated from the mother liquor or dehydrated to obtain the product as a precipitate, as illustrated in step 1302 of FIG. 13. Alternatively, the precipitate is left in the mother liquor and is used as a cementitious composition. Separation of the precipitate can be achieved using any conventional approach, including a mechanical approach, for example, when the bulk of the excess water is drained from the precipitate, for example, either only by gravity or by vacuum, mechanical extraction, by filtering the precipitate from the mother liquor to obtain filtrate, etc. The separation of the bulk of the water gives a wet, dehydrated precipitate. The dewatering unit may be any number of dewatering units connected to each other to dehydrate the suspension (for example, in parallel, in series or in a combined manner).

The above method results in a suspension from the precipitate and the mother liquor. This precipitate in the mother liquor and / or suspension may give a cementitious composition. In some embodiments, part or all of the dehydrated sludge or slurry is further processed to obtain hydraulic cement or additional cementitious compositions.

If desired, compositions consisting of a precipitate and a mother liquor can be stored for a period of time after precipitation and before further processing. For example, the composition can be stored for a period of time in the range of 1 to 1000 days or longer, for example, 1 to 10 days or longer, at a temperature in the range of 1 to 40 ° C., for example, from 20 to 25 ° C.

Then the components of the suspension are separated. Embodiments may include treating the mother liquor if the mother liquor may or may not be present in the same composition as the product. The mother liquor obtained in the reaction can be disposed of as waste using any suitable method. In some embodiments, it can be sent for placement in a settling basin 1307. In some embodiments, it can be placed in a volume of water existing in nature, for example, in the ocean, sea, lake or river. In some embodiments, the mother liquor is returned to a water supply source for the methods of this invention, for example, to the ocean or sea. Alternatively, the mother liquor can be further processed, for example, in accordance with the desalination method, as further described in US Patent Application No. 12/163205, filed June 27, 2008, the description of which is incorporated herein by reference.

The resulting dehydrated sludge is then dried to obtain the carbonate composition of this invention, as illustrated in step 1304 of FIG. 13. Drying can be carried out by air drying the precipitate. When air drying the precipitate, it can be carried out at a temperature in the range from -70 to 120 ° C, if desired. In some embodiments, drying is carried out by freeze-drying (i.e., lyophilization); in this case, the precipitate is frozen, the ambient pressure is reduced, and a sufficient amount of heat is supplied so that the water frozen in the material can sublimate from the frozen precipitate directly into the gas phase. In yet another embodiment, spray drying is used to dry the precipitate; the liquid contained in the precipitate is dried by feeding it through hot gas (for example, a stream of gaseous waste from a power plant), for example, if the liquid is pumped through the spray gun into the main drying chamber, and the hot gas is passed in a direct or counter-flow relative to the direction of the spray . Depending on the specific drying method in the device, the dryer may include a filter element, a freeze drying device, a spray drying device, etc. Air and fine particles 1306 may exit the drying stage.

In some embodiments, the spray drying step may include separating particles of various sizes in the sediment. If desired, the sludge dehydrated product from step 1302 can be washed before drying, as illustrated in step 1303 of FIG. 13. The precipitate can be washed with fresh water, for example, to remove salts (such as NaCl) from the dehydrated precipitate. Used washing water can be disposed of as waste, as is customary, for example, by placing it in settling ponds, etc. The water used for washing may contain metals, for example, iron, nickel, etc.

In some embodiments, the dried precipitate is purified, crushed, aged and / or cured (as shown in purification step 1305), for example, to provide the required physical characteristics, such as particle size, surface area, zeta potential, etc., or to add one or more components to the precipitate, such as impurities, aggregates, additional binders, etc., in order to obtain a carbonate composition. Cleaning may include a wide variety of different methods. In some embodiments, the product is subjected to mechanical refining, for example, grinding to obtain a product with the desired physical properties, for example, particle sizes, etc. The dried precipitate can be crushed or ground to obtain the desired particle size.

In some embodiments, the calcium carbonate precipitate obtained by the methods and devices of this invention is a metastable form, including, but not limited to, laterite, aragonite, amorphous calcium carbonate, or a combination thereof. In some embodiments, the calcium carbonate precipitate obtained by the methods and devices of this invention is in metastable form, including, but not limited to, waterite, amorphous calcium carbonate, or a combination thereof. A vaterite-containing composition of calcium carbonate, after being contacted with water, is converted into a stable polymorphic form, such as aragonite, calcite or a combination thereof, with high compressive strength.

The carbonate composition or binder composition thus obtained has elements or markers that originate from carbon from the carbon source used in the process. These carbonate compositions after setting and solidification have a compressive strength of at least 14 MPa, or at least 16 MPa, or at least 18 MPa, or at least 20 MPa, or at least 25 MPa, or at least 30 MPa, or at least 35 MPa, or at least 40 MPa, or at least 45 MPa, or at least 50 MPa, or at least 55 MPa, or at least 60 MPa, or at least 65 MPa , or at least 70 MPa, or at least 75 MPa, or at least 80 MPa, or at least 85 MPa, or

- 68,024,710 at least 90 MPa, or at least 95 MPa, or at least 100 MPa, or from 14 to 100 MPa, or from 14 to 80 MPa, or from 14 to 75 MPa, or from 14 to 70 MPa, or from 14 to 65 MPa, or from 14 to 60 MPa, or from 14 to 55 MPa, or from 14 to 50 MPa, or from 14 to 45 MPa, or from 14 to 40 MPa, or from 14 to 35 MPa, or from 14 to 30 MPa, or from 14 to 25 MPa, or from 14 to 20 MPa, or from 14 to 18 MPa, or from 14 to 16 MPa, or from 17 to 35 MPa, or from 17 to 30 MPa, or from 17 to 25 MPa, or from 17 to 20 MPa, or from 17 to 18 MPa, or from 20 to 100 MPa, or from 20 to 90 MPa, or from 20 to 80 MPa, or from 20 to 75 MPa, or from 20 up to 70 MPa, or from 20 to 65 MPa, or from 20 to 60 MPa, or from 20 to 55 MPa, or from 20 to 50 MPa, or from 20 to 45 MPa, or from 20 to 40 MPa, or from 20 to 35 MPa, or from 20 to 30 MPa, or from 20 to 25 MPa, or from 30 to 100 MPa, or from 30 to 90 MPa, or from 30 to 80 MPa, or from 30 to 75 MPa, or from 30 to 70 MPa, or from 30 to 65 MPa, or from 30 to 60 MPa or from 30 to 55 MPa, or from 30 to 50 MPa, or from 30 to 45 MPa, or from 30 to 40 MPa, or from 30 to 35 MPa, or from 40 to 100 MPa, or from 40 to 90 MPa, or from 40 to 80 MPa, or from 40 to 75 MPa, or from 40 to 70 MPa, or from 40 to 65 MPa, or from 40 to 60 MPa, or from 40 to 55 MPa, or from 40 to 50 MPa, or from 40 to 45 MPa, or from 50 to 100 MPa, or from 50 to 90 MPa, or from 50 to 80 Pa, or from 50 to 75 MPa, or from 50 to 70 MPa, or from 50 to 65 MPa, or from 50 to 60 MPa, or from 50 to 55 MPa, or from 60 to 100 MPa, or from 60 to 90 MPa or from 60 to 80 MPa, or from 60 to 75 MPa, or from 60 to 70 MPa, or from 60 to 65 MPa, or from 70 to 100 MPa, or from 70 to 90 MPa, or from 70 to 80 MPa, or from 70 to 75 MPa, or from 80 to 100 MPa, or from 80 to 90 MPa, or from 80 to 85 MPa, or from 90 to 100 MPa, or from 90 to 95 MPa, or 14 MPa, or 16 MPa, or 18 MPa, or 20 MPa, or 25 MPa, or 30 MPa, or 35 MPa, or 40 MPa, or 45 MPa. For example, in some embodiments of the above aspects and embodiments, the composition after setting and curing has a compressive strength of 14 MPa to 40 MPa, or 17 MPa to 40 MPa, or 20 MPa to 40 MPa, or 30 MPa to 40 MPa, or from 35 MPa to 40 MPa. In some embodiments, the compressive strength described herein is the compressive strength after 1 day, or after 3 days, or after 7 days, or after 28 days.

Precipitates containing, for example, calcium and magnesium carbonates and bicarbonates, in some embodiments, can be used as building materials, for example, as cements and fillers, as described in U.S. Patent Application No. 12/126776, filed May 23. 2008, which in its entirety is incorporated into the text of this description by reference.

The following examples are provided in order to provide those skilled in the art with a complete disclosure and description of how the invention may be practiced and applied; they do not imply a limitation on the scope of what the inventors consider as their invention; nor is it assumed that the following experiments are all experiments performed or are the only experiments performed. Various modifications of the present invention, in addition to those described in this text, will be apparent to those skilled in the art from the above description and the accompanying drawings. Such modifications are included in the scope of the attached claims. Efforts have been made to ensure accuracy with respect to numbers (e.g., quantities, temperature, etc.); but some experimental errors and deviations should be taken into account. Unless otherwise indicated, fractions represent mass fractions; molecular weight is a weight average molecular weight; temperature is given in degrees Celsius; and the pressure is atmospheric or close to it.

- 69,024,710

In the examples and in other sections of this description, the abbreviations used have the following meanings:

AOM = Anion exchange membrane Hell = Silver Hell / AdS1 = Silver / Silver Chloride cm ² = Square centimeter CE1ON = Chlorethanol CV = Cyclic voltammetry DI = Deionized Edh = Ethylene dichloride G = Gram HC1 = Hydrochloric acid h = Hour Hz = Hertz m = Molar mA = Milliamp mA / cm ² = Milliamp / square centimeter

MG = Milligram min = Minute mmol = Millimole mole = Mole μl = Microliter μm = Micrometer ml = Milliliter ml / min = Milliliter / minute mV = Millivolt mV / s or mVS ' ¹ = Millivolt / second No. C1 = Sodium chloride Jaon = Sodium hydroxide NM = Nanometer Sem ² = Ohm x square centimeter RB / S = Palladium / carbon P1 = Platinum R1-1G = Iridium platinum rpm = Rpm δτγ = Volumetric performance in = Volt mass./about. = Mass / volume mass./mass. = Mass / mass

Examples

Example 1

This example illustrates the experimental setup and the proposed experimental conditions for the reaction in the semi-element. The reaction is carried out in the experimental setup illustrated in FIG. 14. Cyclic voltammetry is carried out in anolytes containing a metal salt (tin chloride (11), chromium chloride (11), iron chloride (11) and copper chloride (1)).

Example 2. Voltage reduction in the presence of CO2 in catholyte.

This example illustrates the highest current density achieved at 0 V in various electrochemical devices. The conditions used for this experiment were as follows: anode: 6 cm ² Ρΐ foil; cathode: 6 cm ² cathode with oxygen depolarization; anolyte: 0.5 M Cr ² + dissolved in ultrapure deionized water; saline: 15.6 wt.% NaCl dissolved in ultrapure deionized water; catholyte: 10 wt.% NaOH dissolved in ultrapure deionized water. The temperature of the solution was kept constant at 70 ° C; the solution was recycled in the cell at 400 rpm using an L1616 peristaltic tube. The electrochemical devices used in this experiment were the electrochemical device 500 shown in FIG. 5A, but with two compartments where only one ion-exchange membrane was used (device A in FIG. 15); the electrochemical device 500 shown in FIG. 5A, with two compartments and CO2 supply to the catholyte (device B in FIG. 15); the electrochemical device 500 shown in FIG. 5A, with three compartments (device C in FIG. 15); and the electrochemical device 500 shown in FIG. 5A, with three compartments and the supply of CO ₂ to the catholyte (device Ό in FIG. 15).

Was bubbled through the catholyte to CO ₂ until the pH value reached not less than 12 and about 10. As illustrated in FIG. 15, adjusting the pH of the catholyte by introducing CO ₂ improved the overall productivity since a higher current density was achieved at 0 V. In addition, removal of the compartment and the cation exchange membrane for the dual-compartment device improved the results compared to the three-compartment device. It is assumed that there is a decrease in ohmic losses due to the membrane and electrolyte.

- 70,024,710

Example 3. Voltage reduction in the presence of CO2 in catholyte.

This example illustrates the highest current density achieved at 0 V in various electrochemical devices. The conditions used for this experiment were as follows: anode: 6 cm ² Ρΐ foil; cathode: 6 cm ² Ρΐ foil; anolyte: 0.5 M Cr ²⁺ dissolved in ultrapure deionized water; saline: 15.6 wt.% ΝαίΊ. dissolved in ultrapure deionized water; catholyte: 10 wt.% ΝαΟΗ dissolved in ultrapure deionized water. The temperature of the solution was kept constant at 70 ° C; the solution was recycled in the cell at 400 rpm using an L1616 peristaltic tube.

The electrochemical devices used in this experiment were an electrochemical device 400 shown in FIG. 4A, but with two compartments in which only one ion-exchange membrane was used (device E in FIG. 16); and the electrochemical device 400 shown in FIG. 4A, with two compartments and CO2 supply to the catholyte (device P in FIG. 16). It should be understood that a similar experiment can be carried out for a device with three compartments, as described in example 2.

Was bubbled through the catholyte to CO ₂ until the pH value reached not less than 12 and about 10. As illustrated in FIG. 16, adjusting the pH of the catholyte by introducing CO ₂ improved overall performance, since it improved voltage by 300 mV at 150 mA / cm ² . In this case, the cathodic reaction produced hydrogen, which can be used to regenerate a metal ion by applying a reaction with hydrogen (as illustrated in FIG. 6). For this test, the current was increased galvanostatically, and the resulting cell voltage was recorded.

Example 4. The treatment of metal with gaseous hydrogen.

Experiment 1. The reaction of chromium with hydrogen.

This example illustrates the reaction of a chromium ion in a higher oxidation state with hydrogen to form a chromium ion in a lower oxidation state and hydrochloric acid. FIG. 17A is an illustration of electrochemical cyclic voltammograms revealing the presence of St ² * after reduction of a 0.46 M St ³ * solution with hydrogen at 25 ° C for 8 hours. Two standard solutions were prepared and electrochemically characterized: 0.46 M Cr ² * and 0 , 46 M St ³ *. The conditions used for this experiment were as follows: anode: 6 cm ² Ρΐ foil; cathode: 6 cm ² Ρΐ foil; Anolyte: 0.46 M Cr ² *, 0.46 M Cr ³ * and a reconstituted solution containing Cr ³ * and Cr ² * dissolved in ultrapure deionized water. The temperature of the solution was kept constant at 70 ° C. A voltage scan was applied from 0 to 0.8 V relative to the reference electrode Lg / LgCl, at a speed of 10 mV / s. In this voltage range, it was supposed to see the oxidation of the Cr ² * standard in the absence of oxidation signals of the Cr ³ * standard. Since an oxidation peak was observed for the Cr ² * standard, a solution reduced from Cr ³ * to Cr ² * was tested using cyclic voltammetry. As illustrated in FIG. 17A, the reduced sample showed the presence of Cr ² *, which indicates the reduction of Cr ³ * to Cr ² * by reaction with hydrogen.

Experiment 2. The reaction of copper with hydrogen.

This example illustrates the reaction of a copper ion of a higher oxidation state with hydrogen to produce a copper ion of a lower oxidation state and hydrochloric acid. 100 ml of DI water was added to a 100 ml one-neck round bottom flask. Using a T-shaped adapter for introducing gas, air above water was aspirated from the flask and the flask was filled five times with nitrogen. Then, 1.7 g (0.01 mol) of CuCl ₂ -2H ₂ O were added to this oxygen-free water (a 0.1 M solution of CuCl ₂ -H ₂ O was obtained) and the core of the magnetic stirrer. To the resulting light blue liquid was added 300 mg 1% Ρά / C, and this mixture was vigorously stirred under nitrogen. Then, the atmosphere in the flask is 4 times aspirated and replaced with gaseous H ₂ from a rubber chamber and finally stored under positive pressure of H2 with vigorous stirring. After 12 hours, the stirrer was turned off, and an aliquot of approximately 2 ml was collected and filtered through a 0.2 μm filter disk using a 5 ml pipette. The filtrate obtained was clear. As illustrated in FIG. 17B, UV and visible spectroscopy showed approximately 94% conversion of Cu (P) to CuD) (the upper curve corresponds to Cu (P) before the reaction, and the lower curve corresponds to Cu (P) after the reaction), while the solution became noticeable acidic (which indicates the formation of HC1).

Example 5. Obtaining a halogenated hydrocarbon from an unsaturated hydrocarbon.

Obtaining EDC from ethylene using copper chloride.

Experiment 1. This experiment is aimed at the formation of ethylene dichloride (EDC) from ethylene using copper chloride (P).

The experiment was carried out in a pressure vessel. The pressure vessel included an outer jacket, inside of which was a catalyst, i.e. a solution of copper chloride (P), and an inlet for sparging gaseous ethylene through a solution of copper chloride (P). The catalyst solution used in the experiment was 200 ml of 1 M No. C1, 1 M CuCl ₂ and 0.5 ml of 12.1 M HC1. This solution was clear and green. The pressure vessel was heated to 160 ° C. and ethylene gas was passed into the vessel to a pressure of 2.1 MPa (300 psi) for 30 minutes. After the reaction, 71,047,710, it was found that the solution became significantly darker than the initial solution. The product obtained in solution was extracted with 50 ml of pentane and then separated using a separatory funnel. The pentane extract containing EDC was investigated by gas chromatography (GC). FIG. 18 illustrates a peak at an EDC retention time. Other small peaks belong to pentane. FIG. 19 shows that there were no peaks on the CV of the catalyst solution before carrying out the reaction, and the CV of the solution after the reaction showed the presence of oxidation at 0.4 V (for the half cell and reference electrode). Spectrometry of the product in the UV and visible regions gave a concentration of Cu ² + 0.973 M.

Experiment 2. This experiment is aimed at the formation of ethylene dichloride (EDC) from ethylene using copper chloride (11). The experiment was carried out in a pressure vessel. The pressure vessel included an outer jacket, inside of which was a catalyst, i.e. a solution of copper chloride (11), and an inlet for sparging gaseous ethylene through a solution of copper chloride (11). The concentration of reagents was as indicated below in table. II. During the experiments, the pressure vessel was heated to 160 ° C, and ethylene gas was passed into a vessel containing 200 ml of solution under a pressure of 2.1 MPa (300 psi) for 30 min-1 h. Before depressurizing and by opening the vessel was cooled to 4 ° C. The product obtained in solution was extracted with ethyl acetate and then separated using a separatory funnel. An ethyl acetate extract containing EDC was subjected to gas chromatographic (GC) analysis.

Table II

Time, h CuC1 ₂ CuC1 YaS1 HC1, m EDH mg Chlorine- ethanol mg Coeff. using Si (EDH) About. production (3ΤΥ) Mass select .: EDH / ODH + C1E1ON), % 0.5 6 0.5 one 0,03 3909.26 395.13 8.77% 0.526 90.82% 0.5 4,5 0.5 2,5 0,03 3686.00 325.50 11.03% 0.496 91.89%

The formation of dichloropropane from propylene using copper chloride.

This experiment aims to produce 1,2-dichloropropane (DCP) from propylene using copper chloride (P). The experiment was carried out in a pressure vessel. The pressure vessel included an outer jacket, inside of which was a catalyst, i.e. a solution of copper chloride (P), and an inlet for sparging gaseous ethylene through a solution of copper chloride (P). 150 ml of a solution of 5 M CuCl ₂ , 0.5 M CuCl, 1 M NaCl and 0.03 M HC1 were placed in a glass lined pressure vessel with a 450 ml stirrer. After purging the closed vessel with nitrogen, it was heated to 160 ° C. After reaching this temperature, propylene was added to the vessel to increase the pressure relative to the initially existing pressure, mainly due to water vapor, to 0.90 MPa (130 psi). After 15 minutes, additional propylene was added to increase the pressure from 0.83 to 0.97 MPa (120 to 140 psi). After another 15 minutes, the pressure was 0.93 MPa (135 psi). At this point, the reactor was cooled to 14 ° C, the pressure was released and the reactor was opened. Ethyl acetate was used to wash reactor parts, and then it was used as a solvent during extraction. The product was analyzed by gas chromatography, which showed the presence of 0.203 g of 1,2-dichloropropane, which was detected in the phase of ethyl acetate.

Example 6. The use of the ligand.

In order to study the copper system associated with the ligand, a sample was prepared using the ligand - Ν, Ν, Ν, Ν-tetramethylethylenediamine (TMEDA).

TMEDA =

Ν, Ν, Ν, Ν-tetramethylethylenediamine

Various other examples of ligands that have been described in this text are illustrated in FIG. 20. Any of the ligands illustrated in FIG. 20 can be used in the catalytic reactions of this invention. Other examples of ligands are also illustrated in Example 10. The aqueous solution had the following composition: 2.5 M CuCl, 1.0 M CuCl ₂ , 0.5 M CuCl and 2.2 M TMEDA. When the ligand was mixed with the rest of the solution, the brownish color of the solution quickly changed to deep blue, which indicates the addition of the ligand (complex formation). Treatment of the above (diluted) solution with dichloromethane followed by vigorous shaking showed that, after phase separation, the complex did not transfer to the extraction solvent. This effect is desirable since it can reduce the contamination of the metal complex if the extraction method is used to separate organic products from metal ions. With the addition of a ligand, the pH of the solution changed from acidic to slightly alkaline (from 2.6 to 7.8 pH). This pH effect of the ligand may be beneficial to reduce the corrosive nature of the copper chloride (P) chloride based catalyst system.

- 72,024,710

Example 7. The decrease in voltage due to the ligand.

The reaction in the semi-element was carried out using the metal-ligand solution from Example 6 and the apparatus of Example 1. The working electrode for carrying out the reaction in the semi-element was an anode of Ρΐ 52 mesh mesh with an area of 4 cm ² ; the counter electrode was Ρΐ foil with an area of 6 cm ² ; and the reference electrode was a saturated calomel electrode (NCE). The solution in a beaker was kept at 70 ° C. In one of the experiments, the solution contained 2.5 M NaCl, 1.0 M CuCl ₂ and 0.5 M CuCl, and did not contain a ligand. In another experiment, the solution contained 2.5 M NaCl, 1.0 M CuCl ₂ , 0.5 M CuCl and 2.2 M TMEDA (Example 6). As illustrated in FIG. 21, a voltage decrease of approximately 200 mV was observed at 150 mA / cm ² if a ligand was used in the metal solution.

Example 8. The decrease in voltage due to the ligand.

The complete reaction in the cell was carried out using the metal-ligand solution from Example 6 and the cell shown in FIG. 4A. Cell components are commercially available; they included an anode of Ρΐ mesh; fine cathode cathode; an anion exchange membrane such as ANA; and a cation exchange membrane, such as 2100. The catholyte was 10 wt.%, solution No. GON. In the first experiment the anolyte was a №S1 2.5 M, 1.0 M and 0.5 SiS1 ₂ M SiS1, and contained no ligand; and in the second experiment, the anolyte was 2.5 M # C1, 1.0 M CuCl ₂ , 0.5 M CuCl and 2.2 M TMEDA (Example 6). FIG. 22 illustrates that the presence of a ligand decreased the redox potential (in this experiment by approximately 300 mV), which led to a decrease in the voltage across the cell. The color of the ligand solution also changed sharply, which could happen due to the oxidation of Cu + to Cu ²⁺ .

Example 9. Anion exchange membrane.

This example illustrates the effect of AOM selection on preventing metal ions from passing through the AOM to the middle compartment. This example also illustrates the choice of AOM, which prevents the transition of metal ions, clogging of the membrane and an increase in resistance.

DC method.

In this experiment, a series of anion-exchange membranes were tested, including AC8, AFM, and ANA from Achot SotrotaDop; RAV and RAR from RIMATES; and Όδν from AzA O1a88. The anion exchange membrane was placed between the anolyte containing 3 M SiS1 _2/1 SiS1 M / 4.6 M №S1, and a chamber containing an electrolyte of 4.6 M №S1. A standard three-electrode design was used, including a working / auxiliary electrode of a platinum grid and a saturated calomel electrode (NCE) as a reference electrode. Two additional NCEs were placed in the Luggin capillary on each side of the membrane. Small current steps 1 were applied; 2; 4; 5; 7.5; 10 and 11 mA / cm ² ; a multimeter was used to record potential changes between the two NKEs. The slope of the dependence of current density on voltage changes is equal to the resistance to the passage of current through the surface area of the membrane. The results are illustrated in FIG. 23. The resistance values in FIG. 23 include resistance of AOM and solution. ACδ, AFM and RAV showed the highest resistance. It is believed that these AOMs were designed for increased blocking of protons, and they require a strongly acidic environment for proper functioning. PAP, Όδν and ANA had a resistance that was lower than more than 5 ohm-cm ² . PAP and Όδν showed noticeable signs of the penetration of Cu-based particles. It was found that ANA is the most effective in preventing the passage through the membrane, and has the lowest resistance.

The method of impedance spectroscopy.

In this experiment, an assembly of two Ρΐ foil electrodes was used. An ANA membrane was placed between brine and Cu-based electrolyte. The frequency range was from 15,000 Hz to 0.001 Hz with an amplitude of 20 mA, and the DC signal was 150 mA / cm ² . The experiment was carried out with and without a cell containing an ANA membrane; and the difference in values at the points of intersection with the X axis in the high-frequency region was the resistivity of the AOM per unit area.

The ANA resistance in three different Cu-based electrolytes is summarized in table. III. Solution A: 4.6 M No. C1; Solution B: 0.5 M CuCl / 2.5 M No. C1; solution C: 4.5 M CuCl ₂ / 0.5 M CuCl / 2.5 M No. C1; and solution Ό: 4.5 M CuCl ₂ / 0.5 M CuCl.

Table III

The set of results of measurements of the resistance of the ANA membrane in various solutions based on Cu

Chemical composition Ohm-cm ^ for solution Ohm cm ² for ANA + solution Ohm-cm ^ for ANA Voltage reduction at 150mA / cm ² A-membrane-A 1.28 3.14 1.86 0.28 A-membrane-B 1.28 / 1.77 3,58 1.81-2.06 0.272-0.308 A-membrane-C 1.28 / 2.8 4.96 2.16-2.92 0.324-0.438 A-membrane-ϋ 1.28 / 3.14 7.51 4.37-5.3 0.656-0.795

It was observed that solution B, in which there was no CuCl ₂ , had a resistance similar to a solution containing only No. Cl ₁ without added CuCl _x . Solution C showed a voltage drop of 320-430

- 73,024,710 mV. The addition of CuCl ₂ to the anolyte gives a slight increase in resistance. It is suggested that this may be the result of a change in the resistance of the solution in AOM. Solution Ό, which is equivalent to solution C, but in the absence of No. C1. showed a more than twofold increase in voltage reduction. It is believed that a change in the nature of copper-containing particles could lead to an increase in resistance.

Permeability or ability of Cu-chloride complexes to penetrate through the membrane.

To measure the passage of Cu-containing particles through the AOM, the complete cell configuration was used. A solution of 4.5 M CuCl ₂ / 0.5 M CuCl / 2.5 M NaCl was supplied to the anolyte; 4.6 M NaCl was fed into the intermediate compartment; and 10 wt.% ΝαΟΗ was fed to the catholyte at 70 ° C. The cell operated at 150 mA / cm ² and 300 mA / cm ² , with several flow rates. For each flow rate (for example, 20 ml / min, 40 ml / min, etc.), the concentration of copper ion was measured before testing and after the cell was operated for 30 minutes. To measure the total content of Cu in the saline solution in the intermediate compartment, before and after the test, spectrometry in the UV and visible regions was used. This value was then compared with the amount of electricity (the number of moles according to Faraday) skipped to obtain a certain percentage of detention. The results are shown in FIG. 24. As illustrated in FIG. 24, the ANA membrane provided more than 99% ± 0.01% retention of all Cu particles, in all cases.

Example 10. The use of the ligand.

49 mg (0.5 mmol) of CuCl was added to a 4 ml glass screw-cap test tube containing a magnetic stir bar. A ligand was added to this solution along with 100 μl of water, and the reaction mixture was allowed to react for 2-3 hours at room temperature. Then added 2 ml of an aqueous solution of 6 M CuCl ₂ and 1 M No. C1, which was heated until complete dissolution. The tube was closed with a pre-notched membrane made of TEP and silicone. The tube was placed in a double-wing high-pressure reactor placed on a tile of a magnetic stirrer with heating. The atmosphere inside the reactor was replaced by Ν2. Stirring was started at 620 rpm, and the reactor was heated to 140 ° C. After reaching the reaction temperature, the pressure in the reactor with numerous tubes inside brought to a total pressure of 2.4 MPa (350 psi). After 1 h, the reactor was cooled to a temperature below 30 ° C and the pressure was slowly released. The reaction mixture was extracted with 1 ml of ethyl acetate. The organic phase was analyzed by gas chromatography (GC) for the content of ethylene dichloride and chloroethanol (C1EUN). FIG. 25A and tab. IV illustrate the specific ligand, the amount of ligand, reaction conditions, and the amount of basic products formed. A comparative example without a ligand is also provided. FIG. 25B illustrates other examples of ligands that can be used in a catalytic reaction. Tab. IV demonstrates that the ligand not only increases the yield of EDC in the reaction, but also increases the selectivity.

Table IV

Ligand number Qty ligand mmol Edh (GC method), mg / ml ΟΙΕίΟΗ (GC method), mg / ml Selectivity No ligand n / a 10,20 1,53 0.87 2 0.5 6.89 1.33 0.84 2 2 3.87 1.15 0.77 3 0.5 8.20 1.48 0.85 3 2 11.56 1.73 0.87 4 0.5 7.84 1.38 0.85 4 2 1.75 0.46 0.79 5 0.5 7.75 1.36 0.85 5 2 2.11 0.70 0.75 6 0.5 15.49 1.78 0.90 6 2 16.29 1.98 0.89 7 0.5 13,42 1.44 0.90 8 0.5 6.88 0.97 0.88 10 0.5 10.14 1.66 0.86 10 2 15.96 1,59 0.91 eleven 0.5 11.10 1.93 0.85 eleven 2 12.22 2.01 0.86 12 0.5 9.75 1,50 0.87 12 2 1.06 0.45 0.70

Example 11. Oxidation of iron in an electrochemical cell.

The reaction in the half cell was carried out using an iron solution, with the installation shown in example 1. The working electrode for the reaction in the half cell was a grid of P1-1t, 152 mesh, 6 cm ² ; the counter electrode was P1 foil with an area of 8 cm ² ; and the reference electrode was a standard hydrogen electrode (SHE) Ag / AgCl. The solution in a beaker was kept at 70 ° C. In this experiment, the solution contained 1 M FeCl ₃ and 2.5 M No. C1. As illustrated in FIG. 26, the oxidation of Fe ² ′ to Fe ³ + at the anode was observed at a voltage scan rate of 5 mV / s.

- 74,024,710

Example 12. Electrolytes in an electrochemical cell.

The complete reaction in the cell was carried out using sodium chloride and ammonium chloride as electrolytes. Cell components are commercially available; they included an anode of Ρΐ mesh; mesh cathode ROM; ANA anion exchange membrane from Leo8er1a; and EnroSh N2100 cation exchange membrane. The catholyte was 10 wt.%, Solution No. YUN. In the first experiment, the anolyte was 4.5 M CuCl ₂ / 0.5 M CuCl / 2.5 M No. C1, and in the second experiment, the anolyte was 4.5 M CuCl ₂ / 0.5 M CuCl / 2.5 M Ν4 ₄ Ο. The solution in the cell was kept at 70 ° C. FIG. 27 illustrates that although both electrolytes, both sodium chloride and ammonium chloride, worked well in an electrochemical cell, anolyte ΝΟ-ιΟ lowered the operating voltage of the cell by 200-250 mV / cm ² at 300 mA / cm ² Assume that may be due to the increased electrical conductivity of the anolyte, which led to a lower resistance of the AOM.

Example 13. Conditioning AOM when starting an electrochemical cell.

This experiment was related to conditioning AOM before starting an electrochemical cell. The initial solution introduced into the full cell was 0.5 M 8O _№-4 as the anolyte, 4.6 M ΝαΟ in the intermediate compartment and 10 wt.% NaOH solution as catholyte. The membranes were PAg from RiMaTesB as an anion exchange membrane and N2100 from EnroSh as a cation exchange membrane. Then the cell was launched at 300 mA / cm ² . At this point, the anodic reaction was oxygen evolution, and the cathodic reaction was water reduction. As illustrated in FIG. 28, an initial total voltage across the cell of approximately 4.5 V was observed. After stabilizing the voltage, the valve was opened and No.-b8O4 was released from the cell, and then anolyte (4.5 M CuCl2 / 0.5 M CuCl1 / 2.5 M No. C1). During this time, the cell was constantly maintained at 300 mA / cm ² . Now, the anodic reaction was an oxidation of copper, as illustrated in FIG. 28 as a sharp decrease in cell voltage. The black curve shows the voltage when introducing copper electrolyte into the cell (without initial voltage stabilization with sodium sulfate) before applying voltage. When using # -b8O4 at startup, the voltage drop was approximately 200 mV, and the voltage was much more stable during the test. Conditioning AOM at a working current density before introducing a copper-based electrolyte can be beneficial for voltage and stability.

Example 14. Recirculation of the aqueous phase from a catalytic reactor into an electrochemical device.

This example illustrates the recirculation of a solution of Cu () obtained in a catalytic reactor, in an electrochemical cell containing an electrode of Ρΐ-1τ grid. A solution containing 4.5 M Cu (P), 0.1 M Cu ^) and 1.0 M No. C1 was loaded into the reactor (Parr bomb) for 60 min, the reaction was carried out at 160 ° C and 2.3 MPa ( 330 psi). The same solution was checked using anodic cyclic voltammetry (CV) before and after the catalytic reaction, to determine the effect of residual organic substances, for example, EDC, or residual extractant on the characteristics of the anode. Each CV experiment was carried out at 70 ° C with a sweep speed of 10 mVs ^-1 , for five cycles, from 0.3 to 0.8 V relative to the saturated calomel electrode (NCE).

FIG. 29 illustrates the obtained current-voltage response of the electrode from the S-1τ grid (6 cm ² ) in solutions before and after the catalytic reaction (indicated, respectively, before and after). As illustrated in FIG. 29, the redox potential (voltage at zero current) after the catalytic reaction shifted toward lower values, as follows from the Nernst equation with increasing concentration of Cu ^). The increase in the concentration of CuD) was due to the formation of EDC with the regeneration of Cu (T) during the catalytic reaction. The CV curve before the catalytic reaction reaches a limit current of about 0.5 A due to limitations on mass transfer at a low concentration of CuCH. The formation of CD) during the catalytic reaction was noted by a marked improvement in kinetic behavior after the catalytic reaction, illustrated in FIG. 29 in the form of a more gentle and linear slope of the dependence of current on voltage, without reaching the limiting current. No negative effect of residual EDC or other organic substances was observed, as indicated by a typical reversible current – voltage curve obtained in CV after a catalytic reaction.

Example 15. Recycling of the aqueous phase from a catalytic reactor containing a ligand.

This example illustrates the recirculation of a solution of CuO). containing a ligand from a catalytic reactor to an electrochemical cell. 2 ml of a sample of the catalyst solution, after testing in a high-performance catalytic reactor, was sent to a three-electrode micro cell for electrochemical testing using anode cyclic voltammetry (CV), in order to detect the existence of a correlation between the redox potential and the performance of the catalyst. The ligands were as follows:

- 75,024,710

The catalyst solution contained 5.0 M Cu (11) / 0.5 M Cu (1) / 0.5 M or 1 M ligand / 1 M IaS1. These ligand solutions were tested in the anode micropowell using cyclic voltammetry, in order to measure the redox potential. The microcell consisted of a working electrode (P £ -1g foil); a counter electrode (Ρΐ foil) and a capillary bridge to the Lg / LgCl microelectrode as a reference electrode. All electrodes were soldered into a 4-ml vessel, heated to 70 ° C and stirred at a speed of 100 rpm. Each CV experiment was carried out at 70 ° C with a sweep speed of 10 mVs ^-1 , for five cycles, from 0.3 to 0.8 V relative to the reference electrode LD / LDSR

The table below V shows the voltages obtained for the five catalytic recycled solutions. The results indicate that the ligand improves the production of EDC, and the catalyst solution recycled to the electrochemical cell containing the ligand reduces the electrochemical voltage. Tab. V shows that the redox potential of samples containing ligand No. 1 (samples A and B) had a lower value compared to the equivalent system E without ligand. Samples C and I, which contained ligand No. 2, had a similar redox potential compared to ligand-free sample E.

Table v

Sample Ligand number Concentration CV BUT one 0.5 0.684 IN one one 0.676 FROM 2 one 0.739 ϋ 2 0.5 0.737 E Ligand missing n / a 0.728

CLAIM

Claims (35)

1. The electrochemical method of halogenation or sulfonation of an unsaturated hydrocarbon or saturated hydrocarbon, comprising bringing the anode into contact with the anolyte, wherein the anolyte contains a metal halide or metal sulfate and salt water; applying voltage to the anode and cathode and oxidizing the metal ion of the metal halide or metal sulfate at the anode from a lower oxidation state to a higher oxidation state; bringing the cathode into contact with the catholyte; halogenating or sulfonating an unsaturated hydrocarbon or saturated hydrocarbon with an anolyte containing a metal ion of a metal halide or metal sulfate in a higher oxidation state in an aqueous medium; while the aqueous medium contains more than 5 wt.% water. 2. The method according to claim 1, further comprising adding a ligand to the anolyte. 3. The method according to claim 1 or 2, further comprising the formation of alkali, water or hydrogen gas at the cathode. 4. The method according to any one of the preceding claims 1 to 3, in which the cathode is selected from a cathode with oxygen depolarization, which reduces oxygen and water to hydroxide ions; a hydrogen gas producing cathode, which reduces water to hydrogen gas and hydroxide ions; producing a hydrogen gas cathode, which reduces hydrochloric acid to hydrogen gas; and a cathode with oxygen depolarization, on which the reaction of hydrochloric acid and gaseous oxygen with the formation of water. 5. The method according to any one of the preceding claims 1 to 4, in which the metal ion in the metal halide or metal sulfate is selected from the group consisting of iron, chromium, copper, tin, silver, cobalt, uranium, lead, mercury, vanadium, bismuth titanium, ruthenium, osmium, europium, zinc, cadmium, gold, nickel, palladium, platinum, rhodium, iridium, manganese, technetium, rhenium, molybdenum, tungsten, niobium, tantalum, zirconium, hafnium and their combinations. 6. The method according to any one of the preceding claims 1 to 5, in which the metal ion in the metal halide or metal sulfate is selected from the group consisting of iron, chromium, copper and tin. 7. The method according to any one of the preceding claims 1 to 6, in which the metal ion in the metal halide or metal sulfate is copper. - 76,024,710 8. The method according to any one of the preceding claims 1 to 7, in which the lower oxidation state of the metal ion in the metal halide or metal sulfate is 1+, 2+, 3+, 4+ or 5+. 9. The method according to any one of the preceding claims 1 to 8, in which the higher oxidation state of the metal ion in the metal halide or metal sulfate is 2+, 3+, 4+, 5+ or 6+. 10. The method according to any one of the preceding claims 1 to 9, in which the metal ion in the metal halide or metal sulfate is selected from copper, which is converted from Cu + to Cu ² +; iron, which is converted from Fe ² + to Fe ³ +; tin, which is converted from 8p ² + to 8p ⁴ +; chromium, which is converted from Cr ²⁺ to Cr ³⁺ ; platinum, which is converted from Ρΐ ²⁺ to Ρΐ ⁴⁺ ; and their combinations. 11. The method according to any one of the preceding claims 1 to 10, in which no gas is used on the anode or no gas is obtained. 12. The method according to any one of claims 1 or 3-11, in which halogenation or sulfonation using a metal ion of a metal halide or metal sulfate at a higher oxidation state results in a halogenated hydrocarbon or sulfonated hydrocarbon, respectively, and a metal ion of a metal halide or metal sulfate to a lower degree of oxidation. 13. The method according to item 12, in which the metal ion of a metal halide or metal sulfate in a lower oxidation state is recycled back to the anolyte. 14. The method according to any one of the preceding claims 1 to 13, in which the anolyte containing a metal ion of a metal halide or metal sulfate in a higher oxidation state, further comprises a metal ion of a metal halide or metal sulfate in a lower oxidation state. 15. The method according to claim 1, in which the unsaturated hydrocarbon is ethylene, which reacts with anolyte containing a metal ion of a metal halide in a higher oxidation state, with the formation of ethylene dichloride. 16. The method according to clause 15, in which in the halogenation reaction additionally formed chloroethanol, trichloroethane, chloral, chloral hydrate, or combinations thereof. 17. The method according to any one of claims 1 or 3-14, in which the unsaturated hydrocarbon is ethylene, propylene or butylene, which reacts with an anolyte containing a metal ion of a metal halide in a higher oxidation state, with the formation of ethylene dichloride, propylene dichloride or 1,4-dichlorobutane, respectively. 18. A method for producing polyvinyl chloride, comprising producing ethylene dichloride according to claim 1, wherein the metal halide is metal chloride and the unsaturated hydrocarbon is ethylene, and further comprising forming vinyl chloride monomer from the obtained ethylene dichloride and forming polyvinyl chloride from vinyl chloride monomer. 19. The method according to any one of claims 1 or 3-14, in which the unsaturated hydrocarbon is a compound of formula I, which after halogenation or sulfonation is converted into a compound of formula II I '(Κ) „, - ϋ _Β Η (; _ο .„, -> (К) „- С _В Н, * _№ <ППЧ |)) I p where η is 2-10; t is 0-5; C.] is 1-5; K is independently selected from hydrogen, halogen, —COOC ′, —OH, and —YAK ′ (K), where K ′ and K are independently selected from hydrogen, alkyl containing from 1 to 10 carbon atoms, and substituted alkyl containing from 1 to 10 carbon atoms and having from 1 to 5 substituents selected from the group consisting of alkenyl, halogen, —OH, —COOH, an amino group and a substituted amino group; X is a halogen selected from chlorine, bromine and iodine; -8O ₃ N or -O8O ₂ OH. 20. The method according to any one of claims 1 or 3-14, in which the saturated hydrocarbon is a compound of formula III, which after halogenation or sulfonation is converted into a compound of formula IV t W IV where η is 2-10; k is 0-5; 8 is 1-5; K is independently selected from hydrogen, halogen, —COOC ′, —OH, and —YAK ′ (K), where K ′ and K are independently selected from hydrogen, alkyl containing from 1 to 10 carbon atoms, and substituted alkyl containing 77,027,710 from 1 to 10 carbon atoms and having from 1 to 5 substituents selected from the group consisting of alkenyl, halogen, —OH, —COOH, an amino group and a substituted amino group; X is a halogen selected from chlorine, bromine and iodine; -8O ₃ N or -O8O ₂ OH. 21. The method according to claim 20, in which the compound of formula III is ethane or propane. 22. The method according to any one of paragraphs. 1 or 3-21, in which the aqueous medium contains from 5 to 90 wt.% Water. 23. The method according to any one of claims 2 to 22, wherein the ligand is selected from the group consisting of substituted or unsubstituted phosphine; substituted or unsubstituted crown ether; substituted or unsubstituted aliphatic nitrogen-containing compounds; substituted or unsubstituted pyridine; substituted or unsubstituted dinitrile and combinations thereof. 24. The method according to any one of claims 2 to 23, in which the ligand has the formula A 1 = 1 And where η and m are independently 0-2; K and K ¹ independently represent H, alkyl containing from 1 to 10 carbon atoms, or substituted alkyl containing from 1 to 10 carbon atoms and having from 1 to 5 substituents selected from the group consisting of alkenyl, halogen, —OH , -COOH, an amino group and a substituted amino group. 25. The method according to any one of claims 2 to 23, in which the ligand has the formula C where K independently represents O, 8, P or Ν; η is 0 or 1. 26. The method according to any one of claims 2-23, in which the ligand has the formula Ό or is an oxide of this compound a ’ϋ where K ¹ , K ² and K ³ independently represent H, alkyl containing from 1 to 10 carbon atoms, substituted alkyl containing from 1 to 10 carbon atoms and having from 1 to 5 substituents selected from the group consisting of alkenyl, halogen, —OH, —COOH, an amino group and a substituted amino group, an alkoxy group that is —O-alkyl, where the alkyl contains from 1 to 10 carbon atoms, a substituted alkoxy group that is —O-alkyl, where the alkyl contains from 1 to 10 carbon atoms and has from 1 to 5 substituents selected from the group consisting of lkenyl, halogen, —OH, —COOH, an amino group and a substituted amino group, aryl containing from 6 to 14 carbon atoms, substituted aryl containing from 6 to 14 carbon atoms and having from 1 to 8 substituents selected from the group consisting of alkyl substituted alkyl, alkoxy, substituted alkoxy, amino, substituted amino, alkenyl, halogen, —OH and —COOH, heteroaryl comprising from 1 to 6 heteroatoms, substituted heteroaryl having from 1 to 6 heteroatoms and having from 1 to 5 substituents, selected from the group consisting of alkyl, substituted ennogo alkyl, alkoxy, substituted alkoxy, amino, substituted amino, alkenyl, halogen, -OH and -COOH, amine, substituted amine that is a group -ΝΕ. ¹⁰ ^ ¹ , where K ¹⁰ and K ^{11 are} independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, cycloalkyl containing from 3 to 14 carbon atoms, substituted cycloalkyl containing from 3 up to 14 carbon atoms and having from 1 to 8 substituents selected from the group consisting of alkyl, substituted alkyl, alkoxy group, substituted alkoxy group, amino group, substituted amino group, alkenyl, halogen, —OH and —COOH, heterocycloalkyl, including from 1 to 5 heteroatoms selected from groups consisting of nitrogen, sulfur and oxygen, and substituted heterocycloalkyl, comprising from 1 to 5 heteroatoms selected from the group consisting of nitrogen, sulfur and oxygen, and having from 1 to 5 substituents selected from the group consisting of alkyl, substituted alkyl , alkoxy, substituted alkoxy, amino, substituted amino, alkenyl, halogen, —OH and —COOH. 27. The method according to any one of claims 2-23, in which the ligand has the formula E - 78,024,710 E where K ¹ and K ² independently represent H, alkyl containing from 1 to 10 carbon atoms, substituted alkyl containing from 1 to 10 carbon atoms and having from 1 to 5 substituents selected from the group consisting of alkenyl, halogen, —OH, —COOH, an amino group and a substituted amino group, aryl containing from 6 to 14 carbon atoms, substituted aryl containing from 6 to 14 carbon atoms and having from 1 to 8 substituents selected from the group consisting of alkyl, substituted alkyl, alkoxygroup, substituted alkoxygroup, amino group, substituted amino group, and lkenyl, halogen, —OH and —COOH, heteroaryl comprising from 1 to 6 heteroatoms, substituted heteroaryl comprising from 1 to 6 heteroatoms and having from 1 to 5 substituents selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy groups, amino groups, substituted amino groups, alkenyl, halogen, —OH and —COOH, amine, substituted amine, which represents the group —ΝΚ ^{| 0} Κ. where K ¹⁰ and K ^{11 are} independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl, cycloalkyl containing from 3 to 14 carbon atoms, substituted cycloalkyl containing from 3 to 14 carbon atoms and having from 1 to 8 substituents selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, amino, substituted amino, alkenyl, halogen, —OH and —COOH, heterocycloalkyl comprising from 1 to 5 heteroatoms selected from groups, co consisting of nitrogen, sulfur and oxygen, and substituted heterocycloalkyl, comprising from 1 to 5 heteroatoms selected from the group consisting of nitrogen, sulfur and oxygen, and having from 1 to 5 substituents selected from the group consisting of alkyl, substituted alkyl, alkoxy groups, substituted alkoxy groups, amino groups, substituted amino groups, alkenyl, halogen, —OH and —COOH. 28. The method according to any one of claims 2-23, in which the ligand has the formula P R G where K represents hydrogen, alkyl containing from 1 to 10 carbon atoms, or substituted alkyl containing from 1 to 10 carbon atoms and having from 1 to 5 substituents selected from the group consisting of alkenyl, halogen, —OH, - COOH, an amino group and a substituted amino group; η is 0-2; t is 0-3; to is 1-3. 29. The method according to claim 1, in which the saturated hydrocarbon is methane. 30. The device for implementing the method according to claim 1, comprising an energy source for applying voltage to the anode and cathode; the anode in contact with the anolyte containing a metal halide or metal sulfate and salt water; cathode in contact with catholyte; a reactor operably connected to the anode compartment; means for supplying an unsaturated hydrocarbon or saturated hydrocarbon and aqueous medium to the reactor; while the aqueous medium contains more than 5 wt.% water. 31. The device according to item 30, in which the anolyte further comprises a ligand, while the ligand is able to interact with a metal ion. 32. The device according to any one of paragraphs.30 or 31, in which the cathode is selected from a cathode with oxygen depolarization, which reduces oxygen and water to hydroxide ions; a hydrogen gas producing cathode, which reduces water to hydrogen gas and hydroxide ions; producing a hydrogen gas cathode, which reduces hydrochloric acid to hydrogen gas; and a cathode with oxygen depolarization, on which the reaction of hydrochloric acid and gaseous oxygen with the formation of water. 33. The device according to any one of paragraphs.30-32, in which the anode is made in such a way that no gas is formed on it. 34. The device according to any one of paragraphs.30-33, in which the metal halide is a copper chloride. 35. The device according to any one of paragraphs.30-34, in which the unsaturated hydrocarbon is ethylene.